1306115 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種用於半導體製造製程中之研磨製程的 . 研磨用組合物之製造方法。 . 【先前技術】 夕於半導體製造領域中，伴隨著半導體元件之微細化以及、 夕層化產生之兩積體化，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 土一化因電極配線等造成之凹凸而重疊層時，則落差變大，籲 且平坦性變為極其不良。又於落差變大之情形時，於光微 衫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 蒸鍍法，Chemical Vapor Dep〇shi〇n)等形成平坦臈之成膜 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。 籲 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_濁有微細粒子㈤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。 91070-970718.doc 1306115 藉由CMP進行平坦化的，裝置主要由旋轉定盤部、載 體部、漿料供給部以及修整部所構成q轉定盤部以黏著 膠帶等將研磨墊貼付於其上面，下面側介由旋轉軸與旋轉 驅動機構連接。載體㈣由切材及護圈環將被研磨物即 石夕晶圓料於其下面，絲圓之加4壓接於研磨塾 上。上面側介由旋轉軸與旋轉驅動機構連接。 、裝料供給部將使氧切、氧化鈽以及氧化料之粒子懸 :蜀於媒質所得之漿料供給至研磨墊表面。修整部具有電附 **有業用金剛石粒子之薄板’並藉由削除研磨屬等附著 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 4 ’並且將聚料供給至研磨塾之大致中央部，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(IntegmedCircuit)晶片之設計規則微細 化’起因於衆料而於石夕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t，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。 〆於氧化硬漿料之原料中，使用氣相式氧化梦或膠體石夕。 氣相式氧切與膠體氧切相比因純度高故而可生成雜質 夕之氧化矽漿料’但凝聚性高且難以實現於媒質中之高八 散化。 。乃 於提高氣相Α氧化石夕之分散穩定性為目的之先前的氣化 矽水料之製造方法中，有於特許第2935125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^ 91070-970718.doc 1306115 之方法。關於任一士、1 法，藉由規定剪切條件以及氧化矽濃 度等以實現穩定之分散性。 辰 實際上，以上述牲4 + ^ 边特5午文獻中所揭示之製造方法製作以$ 相式氧化矽為原料之氧儿收 表作以軋 氧化矽水料時，氧化矽之分散性能不 刀’且漿料中存在較多凝聚物。 【發明内容】 本發明之目的传；^ 、 ’、八—種义散穩定性優良 '凝聚粒子少 之研磨用組合物之製造方法。 夕 本發明係一種研磨用組 含·锢®缺& σ初之i运方法，其特徵在於包 之虱相式氧化矽分散液之第!步驟. 於為使與前錢相式氧切分散液混 後 = :::為特定之。Η值及二氧化-農度_ = 之第2步:添加前述氣相式氧切贿並進行混合 為使則述研磨用組合物之pH值成 10〜3〇重量％而調製前述鹼性物 又本發明之特徵在於： 為8〜12，氧化矽濃度成為 質水溶液。 則述氣相式氧化矽之比表面積為 又本發明之特徵在於 50〜2〇〇 m2/g 0 貝水溶液’其特徵在於：至少 氣氧化鉀、氫氧化鈣、以及氫 種。 又本發明中之前述鹼性物 包含氫氧化錄、氫氧化鈉、 氧化鋇或氫氧化鎂中之任— 根據本發明， 矽分散液。再者 首先於第1步驟击 驟中調製酸性之氣相式氧化 ’較好使用之ϋ如斗斤 孔相式氧化矽之比表面積為 91070-970718.doi 1306115 50〜200 m2/g。 '六其次於第2步驟中，調製驗性物f水溶液。驗性物質水 溶液之濃度以及體積藉由與於第驟中調整之氣相式氧 化石夕分散㈣混合，為使作為目的之研磨用組合物之婦 為 氧化矽浪度成為10〜3 0重量％而調製。再者， 鹼性物質水溶液至少包含氫氧化録、氫氧化鈉、氫氧化 卸'氫氧化甸、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’係於氣相式氧切分散液中 加驗性物質水溶液，但 ’、 、”“ 霄月甲則於已调製之鹼性物質水 洛液中添加氣相式氧化矽分散液。 矾相式氧切分散液之投人㈣，目 剩，故而混合液呈強W ^ 初買水冷液過 石夕、1…/ 生PH值衝擊。然而，因氧化 又*低，故而可抑制凝聚之產生。若 混合液之氧化石夕濃戶上* “山 右繼續投入，則 投入，.、日人r &彳藉由乳相式氧化石夕分散液之 凝聚產Γ 性變4W值衝擊減弱，且可抑制 合:此’可獲得分散穩定性優良、凝聚粒子少之研磨用組 =本發明中之前述第1步驟，其特徵在於包含. 為使初期氧化梦遭度成為46〜54重量。/蔣/ 石夕投入至將PH值調製為i〇〜27之水令。將乳相式氧化 而調製氣相式氧化石夕分散液之步驟；& 雨剪切力 為使氧化石夕漠度成為45〜53重量。/ 相式氧化石夕分散液之步驟’·以及 將水添加至前述氣 91070-970718.doc 1306115 ::吏氧化矽濃度成為33〜44重量％ ’進一步添加水至前 連乳相式氧化矽分散液之步驟。 根據本發明，首先為使初期氧切濃度成為46〜54重量 。而將氣相式氧切投至將_調製為ι()〜2·7之水中，並 供給高剪切力而調製氣相式氧 Μ , 、虱化矽分散液。藉由將pH值調 二·〜·7，可有效供給高剪切力，並可提高分散性。 相使氧化矽濃度成為45〜53重量％，將水添加至氣 式虱化矽分散液。藉由添 . 之黏度降低。 -里水’可使研磨用組合物 最：為使氧化石夕濃度成為33〜44重量％，進—步添加 產生“設定氧切濃度一重量%而可抑制凝聚物 二發明中之前述第2步驟，其特徵在於： 广述氣相式氧切分散液與前述驗性物質水溶液之混 ::本發明，於5小時以内終止前述氣相式 ，述驗性物質水溶液之混合。藉由： 可使混合液之ΡΗ值迅速降低，且可縮 二 乳化石夕易於凝聚之ρΗ值條件 成風相式 又本發明之特徵在於.進牛=可聚產生。 得之研磨用組人物估 乂匕3對前述第2步驟中獲 :磨用組“勿，使用過遽精度為 過濾處理之第3步驟。 、遞益進仃 :::發’於第3步驟t，對於第2步驟 用組合物，使用過慮 度為1〜4 _之過遽器進行過遽處 91070-970718.doc •10· 1306115 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丨〜4 ^爪之過濾器，可有 效除去凝聚物。 【實施方式】 本發明之目的、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。 氧化矽漿料之製造方法大致可分為2個步驟。第丨步驟係 製成酸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PH2,對其供給剪切力並且投人氣相式氧化石夕而 製成分散液。 於第2步驟中，攪拌氧切分散液，並且 等之鹼性水溶液而進行混合。 孔化鉀 =2步驟中’藉由氧切分散液之pH值自 驗性知之PH值衝擊，產生氧化石夕 J化至 分散液之狀態為高滚度氧切， 氧化發 根據本發明，葬吏加易於產生凝聚。 ^藉由改良氧化矽分散液之製藉你丛、 化石夕分散液與鹼性水溶液之混合條件， _ Μ及氧 穩定性優良之氧化矽漿料。 可I造出分散 圖1係本發明一實施方式之流程圖。 首先’對第1步驟進行詳細說明。第 步驟中包含更细微 9l070-970718.doc 1306115 的步驟。 切：步驟1-1中’將超純水之pH值調製為1〇〜27， 刀散裝置供給剪切力，並且投入罝有卜# + 1 且扠八具有比表面積為50〜2〇〇 重量/粉末直至初期氧切濃度成為ΜΑ '〇並以尚剪切分散裝置供給剪切力1〜5小時。 少=Γ，為使氧切濃度成為45〜53重”。，添加 鐘。之超純水至氧切分散液中並供給剪切力10〜4。分 超…，為使氧切濃度成為33〜44重量％，添加 —虱化矽分散液中並供給剪切力05〜4小時。 牛= 述，於第1步驟中，藉由供給高剪切力，並且於 y驟1-2中添加超純水， 度。 J充刀降低氧化矽分散液之黏 人，對第2步驟進行說明。 於步驟2-1中，對於為使 石夕濃度成為H)〜3()重量％而^叙PH值成為8〜12,氧化 一 里0而調製之鹼性物質水溶液中，投 入乳化矽分散液。與先前曰人 之此σ不同，藉由將氧化矽分散 :又：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。 =匕夕刀散液杈入初期’因鹼性物質水溶液過剩，故而 混&液之ΡΗ值呈12〜14之強驗性，且產生ΡΗ值衝擊。但 疋’因氧化石夕濃度非常低，故而可抑制凝聚產生。若繼續 投入，則混合液之氧切濃度上升，但藉由氧化樹液 之投入而混合液之ΡΗ值成為化之弱驗性，故而pH值衝 91070-970718.doc -12- 1306115 擊減弱，並可抑制凝聚產生。 再者，吾人期望於5小時 』晖以内投入全部之氧化矽分锷 液。鹼性物質水溶液之 刀散 .. p值為12〜14，且為氣相式氧化々 之表面溶出之pH值區域。藉此…、* '魏矽 液而可迅速使pH偏移至氧化 散1306115 IX. Description of the Invention: [Technical Field of the Invention] The present invention relates to a method for producing a polishing composition for use in a polishing process in a semiconductor manufacturing process. [Prior Art] In the field of semiconductor manufacturing, with the miniaturization of semiconductor elements and the integration of semiconductor layers, the planarization technology of semiconductor layers or metal layers is an important factor technology. When an integrated circuit is formed on a wafer, if the unevenness is caused by the unevenness of the electrode wiring or the like, the unevenness is increased, and the flatness is extremely poor. Further, in the case where the drop is large, it is difficult to combine the focus on both the concave portion and the convex portion in the light micro-shirt etching method, and it is impossible to achieve miniaturization. Therefore, it is necessary to perform a planarization process for removing irregularities on the surface of the wafer at an appropriate stage in the buildup. In the planarization process, there is an etch back method in which the uneven portion is removed by etching, and a film formation method of forming a flat crucible by plasma cvd (Chemical Vapor Deposition) or the like is performed by heat treatment. A fluidization method for planarization, a selective growth method for depositing a recess by selecting CVD or the like, and the like. In the above method, there is a problem that the area which is suitable or flattenable due to the difference in the type of the film such as the insulating film or the metal film is extremely narrow. As a flattening processing technique that can overcome such a problem, there is a flattening by CMp. According to the planarization treatment of CMP, the slurry is supplied to the surface of the polishing pad by the slurry of the fine particles (5), and the surface of the polishing pad is moved relative to the stone wafer to be highly precise. The ground flattens a wide range of wafer surfaces. 91070-970718.doc 1306115 The device is flattened by CMP, and the device is mainly composed of a rotating platen portion, a carrier portion, a slurry supply portion, and a trimming portion, and the polishing pad is attached thereto by an adhesive tape or the like. The lower side is connected to the rotary drive mechanism via a rotary shaft. The carrier (4) is made of a cutting material and a retainer ring, that is, a stone wafer is placed underneath, and a wire is added to the polishing crucible. The upper side is connected to the rotary drive mechanism via a rotary shaft. The charge supply unit suspends the particles of the oxygen cut, the cerium oxide, and the oxidized material: the slurry obtained by the medium is supplied to the surface of the polishing pad. The trimming portion has a thin plate </ RTI> which is electrically attached to the diamond particles, and the surface of the polishing pad having the low polishing property is regenerated by removing the adhered portion such as the abrasive. The CMP apparatus rotates the rotary disk portion and the carrier 4' by a rotary drive mechanism and supplies the material to a substantially central portion of the polishing pad, and the wafer processing surface is ground by relatively moving the wafer and the polishing pad. In recent years, the design rule of the IC (Integmed Circuit) wafer has been miniaturized. The micro scratches caused by the polished surface of the Shixi wafer have become a problem. As the cause t of the minute scratch, it is considered that there are coarse particles existing in the aggregate or the poor dispersion of the abrasive grains suspended in the medium. In the raw material of the oxidized hard slurry, a gas phase oxidation dream or a colloidal stone is used. Since the gas phase oxygen scavenging is higher in purity than the colloidal oxygen scavenging, it is possible to form an impurity cerium oxide slurry, but the cohesiveness is high and it is difficult to achieve high densification in the medium. . In the prior art method for producing a gasified water-repellent material for the purpose of improving the dispersion stability of the gas phase osmium oxide, it is disclosed in Japanese Patent No. 2935125, No. 2949633, and JP-A No. 2_26771 The method of 91070-970718.doc 1306115 is disclosed in the Gazette. Regarding any of the methods, the method of determining the shearing condition and the concentration of cerium oxide to achieve stable dispersibility. In fact, in the production method disclosed in the above-mentioned animal 4 + ^ Bian special 5 noon literature, the oxygenation of yttrium oxide is not produced when the oxidized cerium is used as the raw material for the oxidation of cerium oxide. Knife' and there is more agglomerate in the slurry. SUMMARY OF THE INVENTION The object of the present invention is to provide a method for producing a polishing composition having a small stability of agglomerated particles. The present invention is a method for polishing a group containing 锢 缺 缺 amp amp amp , , , , , , , , , , , , , , ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! After liquid mixing = ::: is specific. Η 及 二 二 二 二 二 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第Further, the present invention is characterized in that it is 8 to 12, and the cerium oxide concentration becomes a qualitative aqueous solution. Further, the specific surface area of the gas phase cerium oxide is further characterized by the fact that the aqueous solution of 50~2 〇〇 m2/g 0 is characterized by at least potassium oxyhydroxide, calcium hydroxide, and hydrogen species. Further, the above-mentioned basic substance in the present invention contains any of hydrazine hydroxide, sodium hydroxide, cerium oxide or magnesium hydroxide - a hydrazine dispersion according to the present invention. Further, in the first step of the first step, the acidic gas phase oxidation is prepared. The preferred surface area of the ruthenium phase ruthenium is 91070-970718.doi 1306115 50 to 200 m2/g. 'Six followed by the second step, preparing an aqueous solution of the test substance f. The concentration and the volume of the aqueous solution of the test substance are mixed with the vapor phase oxidized oxide (4) adjusted in the first step, so that the target of the polishing composition for the purpose is a cerium oxide wave of 10 to 30% by weight. And modulation. Further, the aqueous alkaline substance solution contains at least one of a hydroxide, a sodium hydroxide, a hydroxide, a hydroxide, and a barium hydroxide or a magnesium hydroxide. According to the previous manufacturing method, the aqueous solution of the test substance is added to the gas phase oxygen-cutting dispersion, but ',,,,,,,,,,,,,,,,,,,,,,,,,,,,, Dispersions. The input of the 矾 phase type oxygen-cut dispersion (4), the remaining, so the mixture is strong W ^ initial purchase of water-cooled liquid over Shi Xi, 1 ... / raw PH value impact. However, since oxidation is also low, the occurrence of agglomeration can be suppressed. If the mixed solution of the oxidized stone is concentrated on the 夕 户 “ “ “ “ “ “ “ “ “ 山 山 山 山 山 山 山 山 山 山 山 山 山 山 山 山 山 山 山 山 山 山 山 山 山 山 山 山 山 山 山 山 山 山It is possible to suppress the combination: This is a polishing group which is excellent in dispersion stability and has few aggregated particles. The first step in the present invention is characterized in that it is included in order to make the initial oxidation dream degree 46 to 54 weight. / Shi Xi is put into the water order to adjust the pH value to i〇~27. The step of oxidizing the milk phase to modulate the gas phase oxidized oxide eve dispersion; & rain shear force is to make the oxidized stone 45~53 weight. / Step of phase oxide oxide dispersion> and adding water to the above gas 91070-970718.doc 1306115: 吏 吏 吏 concentration is 33~44% by weight ' Further adding water to the former milk The step of the phase cerium oxide dispersion. According to the present invention, first, the initial oxygen cut concentration is 46 to 54 by weight, and the gas phase oxygen is cut into water which is prepared to be ι()~2·7, and Supply high shear force to modulate gas phase oxime, bismuth bismuth hydride dispersion. By pH 2·~·7, can effectively supply high shear force and improve dispersibility. The concentration of cerium oxide is 45~53% by weight, and water is added to the gas bismuth hydride dispersion. - The liquefied water can make the polishing composition the most: in order to make the concentration of the oxidized stone to be 33 to 44% by weight, and to add "the oxygen cut concentration is set to 1% by weight, and the agglomerate can be suppressed. The second step is characterized in that: the gas phase oxygen-cut dispersion is mixed with the aqueous solution of the test substance: In the present invention, the gas phase type and the aqueous solution of the test substance are terminated within 5 hours. By: the enthalpy value of the mixed liquid can be rapidly lowered, and the Η 乳化 易于 易于 易于 易于 易于 易于 易于 成 成 成 成 成 成 成 成 成 成 成 成 成 成 成 成 成 成 成 成 成 成 成 成 成 成 成 成The obtained group of grinding figures is estimated to be obtained in the second step: the grinding group "No, the third step of filtering using the precision of using 遽 。., 益益进仃:::发' in the third step t, for the composition for the second step, using a filter with a degree of overcoming of 1 to 4 _, the entanglement is carried out at 91700-970718.doc • 10· 1306115. As described above, the grinding combination obtained in the second step The object is less likely to be agglomerated. Therefore, the use of a filter having a filtration accuracy of 丨4^4 claws can effectively remove the aggregates. [Embodiment] The objects, features, and advantages of the present invention are as described in the following detailed description and The drawings can be more clearly described. The embodiment suitable for the present invention will be described in detail with reference to the following drawings. The method for producing a cerium oxide slurry can be roughly divided into two steps. The second step is a step of preparing an acidic cerium oxide dispersion, the second step. The step of mixing the aqueous solution of the cerium oxide dispersion and the alkaline substance. In the first step, an acid such as hydrochloric acid is added to the ultrapure water to become an acid such as PH2, which is supplied with shearing force and is subjected to a gas phase. Oxide oxide as a dispersion In the second step, the oxygen-cut dispersion is stirred and mixed with an alkaline aqueous solution. Potassium sulphate = 2 steps 'The pH value of the oxygen-cut dispersion is self-inspected to produce an oxidized stone. The state of the dispersion to the dispersion is high rolling oxygen cutting, and according to the present invention, the fungus is easily condensed. ^ By modifying the cerium oxide dispersion, the plexus, the fossil dispersion and the alkaline aqueous solution are used. Mixing conditions, yttrium oxide and yttrium oxide slurry excellent in oxygen stability. Fig. 1 is a flow chart of an embodiment of the present invention. First, the first step will be described in detail. The first step includes finer 9l070. -970718.doc Steps of 1306115. Cut: In step 1-1, 'modulate the pH value of ultrapure water to 1〇~27, the knife-distribution device supplies shear force, and puts in the 罝有卜# + 1 and the fork has The specific surface area is 50~2〇〇 weight/powder until the initial oxygen cut concentration becomes ΜΑ '〇 and the shearing force is supplied by the shearing dispersing device for 1 to 5 hours. Less = Γ, so that the oxygen cut concentration becomes 45~53 ". , add the clock. The ultrapure water is supplied to the oxygen cut dispersion and supplied with a shear force of 10 to 4. In order to make the oxygen cut concentration 33 to 44% by weight, the bismuth telluride dispersion was added and supplied with a shearing force for 05 to 4 hours. Cattle = In the first step, by supplying high shear force, ultrapure water is added in steps 1-2. The J filling knife reduces the stickiness of the cerium oxide dispersion, and the second step will be described. In the step 2-1, the emulsified enamel dispersion is introduced into the alkaline substance aqueous solution prepared by making the pH value of H) to 3 ()% by weight and the pH value is 8 to 12 and oxidizing one mile. . Unlike the σ of the previous monk, the formation of aggregates during mixing can be suppressed by dispersing the cerium oxide: again into an aqueous alkaline solution. The reason is as follows.匕 匕 刀 刀 散 散 ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ 因 因 因 因 因 因 因 因 因 因 因 因 因 因 因However, 疋' can inhibit aggregation due to the very low concentration of oxidized oxalate. If the input is continued, the oxygen cut concentration of the mixed solution rises, but the enthalpy of the mixed liquid becomes weak by the input of the oxidizing sap, so the pH value is weakened by the 91070-970718.doc -12-1306115, and Can inhibit the formation of agglomeration. Furthermore, we expect to put all of the cerium oxide mash in less than 5 hours. The knife solution of the aqueous alkaline solution has a p value of 12 to 14, and is a pH region where the surface of the gas phase cerium oxide is eluted. By using ..., * 'Wei liquid can quickly shift the pH to oxidation
8〜12。 夕拉子之为政穩定區域即pH 如上所述，於第2步驟φ雜丄收— u 中猎由將氧化矽分散液投入至給 性物質水溶液中，可抑制、日 主驗 J抑制作匕合時之凝聚物產生。 經由第1以及第2步驟獲得 付之虱化矽漿料，因凝聚物少， 且黏度低，故而可藉由過據器有效除去凝聚物。 於步驟3-1中，使用過濾精度 Η μηι之過濾器進行過 慮。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)關於氧化矽分散液之pH值 關於步驟Μ中之pH值，於pH值分別為2、3、7之條件 下製成氧化石夕漿料。再者，pH值以外之條件全^目I 圖2係表示PH㈣於凝聚粒子成㈣料_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#料之分散穩定性進行振盛實驗。振蓋實 驗為：將已製成之20 ml氧化矽漿料放至容量5〇如之振盪 管中’設置於縱型振盪機内，# " 並以振盪速度31〇 spm(str〇ke per minute)、振盪衝程4〇 仃振盪，經過 既定時間後取出振蘯管，並使用私由、 使用粒度分佈測定裝置 91070-970718.doc 13- 1306115 (ilORIBA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_振盪前之中間粒子直徑）/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 Π表示pH 7之情形。於pH 2之情形時，可知即使振盪1〇天 粒子直徑亦無變化，且具有較高之分散穩定性。於？11 3之 情形時，可知10天後成長率約為18°/〇 ;於pH 7之情形時， 可知1 0天後成長率約為88%並皆產生凝聚。考慮到其係因 為氣相式氧化矽之等電點位於pH 2附近，故而於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。 刊丨己炒刀散液、，"用乳儿炒濃度 關於步驟1 _ 1中夕3镑备 期氧化矽濃度，將初期氧化矽濃度 、5。重量％、55重”。、以及_%之條 件I成氧化矽漿料。再者 部相同。 d乳化矽濃度以外之條件全 圖3係表示氧化矽分散 漿料粒度分佈之影響圖表 '縱濃度對於氧切 直徑。曲線“表示初期氧化表示粒子 線15表不初期氧切濃度為 里之情形’曲 初期氧化石夕濃度為55重 置’。之情形’曲線16表示 度為6〇重量％之情形。 月形，曲線17表示氧化矽濃 91070-970718.doc -14- 1306115 如圖表所示可知，初期氧化石夕濃度越高則氧 粒度分佈越向左移位，故而初期氧化石夕遭度越高❹= 越高。於初期氧化石夕濃度低為45重量％之情 1 因高剪切分《置之剪切力無法充分傳達，故而= 低。又，於55重量％以及6〇重量％之情形時，努 分傳達故而分散性高，但氧化石夕分散 可充 大對於分散機之負炉故而W度上升，且加 重量%之情：： 於初期氧切濃度為5。 高…可減小對於分散機之負擔，且分散性亦 ^由以上情形’可知較好氧切分散液之 度為46〜54重量％。 乃乳化矽浪 (3)關於添加少量之超純水 關於步驟1_2中之和站|^、兵上 去沐知4 水添加，分別以添加之情形以及 未添加情形之條件製成 外之條件全部相同。 再者添加超純水以 =未添加少量之超純水之情形時，氧化矽漿料之中門粒 子直徑與已添加之情形相比變大。 二 切力越易於傳逵，m 晨度越向男 故而未添加之情形之分散性低，且氧 矽漿料之黏度上升約4%。 且乳化 藉由以上*陰形 分散液中，’可知較好是添加少量之超純水至氧化石夕 氧化矽濃度設定為45〜53重量％。 (4)關於氧化石夕分散液之氧化石夕濃度 關於步驟1_3 φ 重量％、重量。/ 4 分別以氧化石夕濃度為32 1。、45重量％以及49重量％(未添加超純水） 91070-970718.doc •15- 1306115 再者，氧化矽濃度以外之條件全 之條件製成氧切漿料 部相同。 口，㈣氧切濃度對於氧切 之影響圖表，表示粗大粒子數，橫轴二 =子數 曲綠1 -— 惯釉表不粒子直徑。 氧化石夕、，農产匕石幻農度為32重量％之情形，曲線19表示 45重，：Γ〇重量%之情形’曲線2°表示氧切漠度為 形。：二！形’曲線21表示氧㈣濃度為49重量。之情 Η子直徑大於〇·5㈣之粒子作為粗大粒子，計算含 有各粒子直徑之粒子數。 與氧化矽漢度為32重量％、45重量％以及49重量％之情 形相比較，氧化石夕濃度為4〇重量％之情形時之粗大粒子數 最少。可認為其係因為4〇重量％時之黏度可最有效地施加 分散機之#切力。因此’可認為氧化石夕濃度為32重量％之 ㈣時黏度低’於45重量％、49重量％時黏度過高。 藉由以上情形’可知較好二氧化石夕分散液之氧化石夕濃度 為33〜44重量％。 (5)關於氧化石夕分散液與驗性物質水溶液之混合條件 關於步驟Μ中之氧化矽分散液與鹼性物質水溶液之混 合中’分別以將驗性物質水溶液投人至氧切分散液之情 形（第1混合條件）’以及將氧化石夕分散液投入至驗性物質水 浴液之情形（第2混合條件）的條件，製成氧化矽漿料 。作為 驗性物質’使用氫氧化鉀。再者，混合條件以外之條件全 部相同。 圖5係表不混合條件對於氡化矽漿料之粒度分佈之影響 91070-970718.doc *· 16 · 1306115 圖表^縱轴表示頻率，橫轴表示粒子直徑。曲線22a、22b 表不第1混合條件之情形，曲線23表示第2混合條件之情 形。 如則所述第1混合條件之情形時pH值衝擊變大，並易產 生凝聚物。實際上，於粒度分佈中可見在Η _附近凝聚 物產生之峰值。相對地，根據第2混合條件，可見粒子直 徑位於(Μ _附近突現之峰值’且可知分散性得以提高。 亦對氧化石夕衆料之中間粒子直徑進行測定。混合前之 氧化石夕分散液之中間粒子直徑為u〇 nm。以第U合條件 混合乳化石夕分散液與氫氧化鉀水溶液時之氧化石夕聚料之中 7粒子直徑成為觀·，並存在有非常大之凝聚物。對 I:可知以第2混合條件混合時之氧化㈣料之中間粒子 直住維持為丨10 nm則幾乎無凝聚產生。 藉^上情形’混合氧切分散液與驗性物質水溶液之 ^時’可知將氧切分散液投人至驗性物質水溶液中較 (6)關於氧化矽分散液之投入時間 時π驟_驗性物質水溶液投入氧切分散液之 時間’ W5小時投人全部之氧切分散液之情带、 以及於2〇分鐘投人之情㈣條件1錢化 / 鹼性物質，使用氫氧化鉀。再者 7 作為 部相同。 _㈣子又入時間以外之條件全 圖6係表示氧切分散液投人時 度分佈之影響圖表11匕梦漿料之粒 表縱轴表不頻率，橫轴表示粒子直徑。 91070-9707I8.doc 1306115 曲線25表示投入時 曲線24表示投入時間為5小時之情形 間為20分鐘之情形。 若長時間投人氧切分散液’則因氫氧化鉀水溶液為強 鹼性’故而因pH值衝擊產生凝聚物。藉 混合液之PH值可迅速降低至氧化耗定區域，即以 下’故而可抑制凝聚物產生。 藉由以上情形，可知於驗性物質水溶液投入氧化石夕分崩 液，較好是於5小時以内終止。 月8~12. As for the political stability zone, the pH is as described above. In the second step, the cerium oxide dispersion is put into the aqueous solution of the donor substance, which can suppress and suppress the daily test. The condensate produced at the time. The bismuth telluride slurry obtained by the first and second steps has a small amount of aggregates and a low viscosity, so that the aggregate can be effectively removed by a passer. In step 3-1, the filter with filter accuracy Η μηι is used for care. Thereby, the treatment can be carried out at a flow rate of 2 to 10 liters/min, and a sufficient treatment flow rate can be maintained, and coarse particles can be removed. Hereinafter, the results of the discussion on the respective step conditions will be described. (1) About the pH value of the cerium oxide dispersion The pH value in the step , was made into a oxidized stone slurry under the conditions of pH values of 2, 3, and 7, respectively. In addition, the conditions other than the pH value are all shown in Fig. 2, which shows that PH (four) is formed into a (four) material_table. 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 oxidation # material, a vibrating experiment was carried out. The vibrating lid experiment is: put 20 ml of cerium oxide slurry which has been prepared into a volumetric vessel of 5 〇 such as a oscillating tube, set in a vertical oscillating machine, # " and at an oscillation speed of 31 〇spm (str〇ke per minute) ), the oscillation stroke is 4 〇仃 oscillation, after a predetermined time, the vibrating tube is taken out, and the cerium oxide slurry is measured using a particle size distribution measuring device 91070-970718.doc 13-1306115 (manufactured by ilORIBA: model LA-910). Median particle diameter. The growth rate of the agglomerated particles was calculated by (the intermediate particle diameter after the oscillation - the diameter of the intermediate particles before the oscillation) / the intermediate particle diameter before the oscillation χ 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 Π indicates the case of pH 7. In the case of pH 2, it was found that the particle diameter did not change even after shaking for 1 day, and had high dispersion stability. to? In the case of 11 3, it can be seen that the growth rate after 10 days is about 18°/〇; at the case of pH 7, it is known that the growth rate after about 10 days is about 88% and both of them are agglomerated. Considering that the isoelectric point of the gas phase yttrium oxide is located near pH 2, the particle surface becomes electrically neutral at 2 o'clock, and high shear force is easily applied. From the above, it is understood that the pH of the cerium oxide dispersion is preferably from 1 to 2.7.丨 炒 炒 炒 、 、 、 、 、 、 、 、 、 、 、 、 、 关于 关于 关于 关于 关于 关于 关于 关于 关于 关于 关于 关于 关于 关于 关于 关于 关于 关于 关于 关于 关于 关于 关于 关于 关于The conditions I of the weight %, 55 weights, and _% are bismuth oxide slag. The same is true. The conditions other than the emulsified cerium concentration are shown in Fig. 3, which shows the influence of the particle size distribution of the cerium oxide dispersion slurry. For the oxygen cut diameter, the curve "indicates that the initial oxidation indicates that the particle line 15 does not indicate the initial oxygen cut concentration." The case 'curve 16 indicates a case where the degree is 6 〇 wt%. Moon shape, curve 17 indicates yttrium oxide concentration 91070-970718.doc -14-1306115 As shown in the table, the higher the initial concentration of oxidized oxide, the more the oxygen particle size distribution shifts to the left, so the initial oxidation of the oxidized stone is higher. ❹ = higher. In the initial stage, the concentration of oxidized rock is as low as 45% by weight. 1 Because of the high shear fraction, the shear force cannot be fully conveyed, so = low. Further, in the case of 55% by weight and 6% by weight, the dispersion is high, but the dispersion of the oxidized stone can be increased to the negative furnace of the disperser, and the W degree is increased, and the weight is increased by: The initial oxygen cut concentration was 5. The height can reduce the burden on the dispersing machine, and the dispersibility is also from the above case, and the degree of the oxygen-cutting dispersion is preferably from 46 to 54% by weight. It is emulsified 矽 ( (3) about adding a small amount of ultrapure water. In the step 1_2, the station is provided with the same conditions as the conditions of the addition and the conditions of the unadded conditions. . Further, when ultrapure water is added to = when a small amount of ultrapure water is not added, the diameter of the gate particles in the cerium oxide slurry becomes larger than that in the case where it has been added. The second force is more likely to be transmitted, and the dispersibility of the case where the morning is not added to the male is low, and the viscosity of the oxon slurry is increased by about 4%. Further, emulsification is carried out by the above *female dispersion, and it is understood that a small amount of ultrapure water is added to the oxidized cerium oxide concentration of 45 to 53% by weight. (4) About the oxidized oxide concentration of the oxidized oxide dispersion, regarding step 1_3 φ by weight, weight. / 4 The concentration of oxidized stone is 32 1 respectively. 45 wt% and 49 wt% (no ultrapure water added) 91070-970718.doc • 15-1306115 Further, the conditions other than the cerium oxide concentration are the same as those of the oxygen cut slurry. Mouth, (d) The effect of oxygen cut concentration on oxygen cut, showing the number of coarse particles, the horizontal axis two = the number of sub-curves 1 - the glazed table is not the particle diameter. In the case of oxidized stone, the auxinism of the aragonite is 32% by weight, the curve 19 represents 45 weights, and the case where Γ〇 Γ〇 is %. The curve 2° indicates that the oxygen mitosis is shaped. :two! The shape 'curve 21 indicates that the oxygen (tetra) concentration is 49% by weight. The particles whose diameter is larger than 〇·5 (4) are used as coarse particles, and the number of particles containing the diameter of each particle is calculated. Compared with the case where the cerium oxide is 32% by weight, 45% by weight, and 49% by weight, the number of coarse particles is the smallest when the concentration of the oxidized oxide is 4% by weight. It can be considered that the viscosity of the crucible can be most effectively applied by the viscosity at 4% by weight. Therefore, it can be considered that the concentration of the oxidized stone is 32% by weight, and the viscosity is too low at 45% by weight and 49% by weight. From the above, it is understood that the concentration of the oxidized stone in the dispersion of the cerium oxide is preferably from 33 to 44% by weight. (5) Regarding the mixing conditions of the oxidized oxide dispersion and the aqueous solution of the test substance, in the mixing of the cerium oxide dispersion and the aqueous alkaline solution in the step ', respectively, the aqueous solution of the test substance is administered to the oxygen-cut dispersion In the case (first mixing condition) and the condition in which the oxidized oxide dispersion liquid is supplied to the aqueous bath of the test substance (second mixing condition), a cerium oxide slurry is prepared. As the test substance, potassium hydroxide was used. Furthermore, the conditions other than the mixing conditions are all the same. Figure 5 shows the effect of the non-mixing conditions on the particle size distribution of the bismuth telluride slurry. 91070-970718.doc *· 16 · 1306115 The graph ^ vertical axis represents frequency and horizontal axis represents particle diameter. The curves 22a and 22b show the case of the first mixing condition, and the curve 23 shows the case of the second mixing condition. In the case of the first mixing condition, the pH value becomes large, and aggregates are easily generated. In fact, the peak of the condensate produced near Η _ can be seen in the particle size distribution. On the other hand, according to the second mixing condition, it can be seen that the particle diameter is located at (the peak value near the vicinity of Μ _) and the dispersibility is improved. The diameter of the intermediate particle of the oxidized stone mass is also measured. The oxidized oxide dispersion before mixing The diameter of the intermediate particles is u 〇 nm. The diameter of the 7 particles in the oxidized oxidized granules when the emulsified diarrhea dispersion and the potassium hydroxide aqueous solution are mixed under the conditions of the U-component is observed, and there is a very large aggregate. For I: it can be seen that when the intermediate particles of the oxidized (four) material are mixed under the second mixing condition and maintained at 丨10 nm, almost no agglomeration occurs. By the case, the 'mixed oxygen-cut dispersion and the aqueous solution of the test substance' It can be seen that the oxygen cut dispersion is injected into the aqueous solution of the test substance. (6) When the input time of the cerium oxide dispersion is π, the time when the aqueous solution of the test substance is put into the oxygen cut dispersion is taken. The feeling of the dispersion, and the investment in 2 minutes (4) Condition 1 money / alkaline substance, use potassium hydroxide. In addition, 7 is the same as the part. _ (four) sub-entry time conditions full figure 6 shows oxygen Effect of Dispersion Investment Time Distribution Chart 11 The miracle slurry has a vertical axis indicating no frequency, and the horizontal axis indicates particle diameter. 91070-9707I8.doc 1306115 Curve 25 indicates that the input curve 24 indicates that the input time is 5 hours. In the case of 20 minutes, if the oxygen-cutting dispersion is injected for a long time, the aqueous solution of potassium hydroxide is strongly alkaline, so the aggregates are generated by the pH impact. The pH of the mixture can be rapidly reduced to the oxidation rate. In the above-mentioned case, it is possible to suppress the generation of aggregates. In the above case, it is known that the aqueous solution of the test substance is supplied to the oxidized stone, which is preferably terminated within 5 hours.
圖7係表示氧化石夕分散液投入速度對於混合液之p Η值之 影響圖表。縱轴表示混合液之ΡΗ值，橫軸表示氧化石夕分散 液之技入日守間。曲線26表示投入速度為升/分鐘之情 形，曲線27表示投人速度為12.5升/分鐘之情形，曲線28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)關於過遽器之過濾精度以及處理流速Fig. 7 is a graph showing the effect of the input speed of the oxidized oxide dispersion on the p Η value of the mixed liquid. The vertical axis represents the enthalpy of the mixed solution, and the horizontal axis represents the technical entanglement of the oxidized oxide dispersion. Curve 26 indicates the case where the input speed is liter/minute, curve 27 indicates the case where the input speed is 12.5 liters/min, and curve 28 indicates the case where the input speed is 5 liters/min. Thus, by accelerating the input speed, the pH of the mixed solution can be quickly lowered to a stable yttrium oxide region, i.e., pH 12 or lower. _ (7) About the filter accuracy of the filter and the processing flow rate
百先，關於步驟3_1中之過濾器之過濾精度，分別以過 、思月又為1 、3 、5 、7 以及1 之條件進行 過滤'。至於過據器’使用壓力損失小並可獲得大流量之深 度型過濾器。 圖8係表不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;慮處理雨之粗大粒子數、以及過濾處理後之粗大粒子 數°直線29表示過濾精度為1 μιη之情形時之粒子數變化， 91070-970718.doc •18· 1306115 直線30表示過濾精度為3 μηι之情形時之粒子數變化，直線 3 1表示過濾精度為5 μπι之情形時之粒子數變化，直線3 2表 不過濾精度為7 μηι之情形時之粒子數變化，直線33表示過 據精度為1 0 μιη之情形時之粒子數變化。 過濾精度為5 μηι、7 μηι、1 〇 μηΐ2情形時，因過濾精度 大於粗大粒子之粒子直徑，故而過濾處理後之粗大粒子數 幾乎無變化，且無法獲得充分之過濾性能。對此，過濾精 度為1 μιη、3 μιη之情形時，過濾處理後之粗大粒子數大幅 度減少。 其次，關於步驟3 -1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 軸表示過濾處理之處理流速，圖中表示針對於各過濾精度 之處理流速。符號74表示過濾精度為i μιη之情形時之流 速，符號75表示過濾精度為3 之情形時之流速，符號％ 表示過濾精度為5 μιη之情形時之流速，符號77表示過濾精 度為7 μπ!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，故而過濾精度為1 μηι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 濾精度為1〜4 pm之過濾器即可。此時之處理流速成為2〜ι〇 升/分鐘。 91070-970718.doc -19- 1306115 其次，關於基於先前技術而製 基於本發明而製忐 先則巩化矽漿料、與 而裟成之虱化矽漿料（以下盤盔「麻 比較結果進行說明。第i個先仏μ稱為實施例!」）的 較m」）係基於特 ’b矽黎料(以下稱為「比 號公報所揭示之製造方法 先刖虱化矽漿料（以下稱「 成氧化石夕濃产t卜笛1>fm * 車父例2」）製造 明L: 先前氧化”料低，且與基於本發 月製成之氧化㈣料#同#程度之黏度。 實施例1係根據以下步驟製成。Bai Xian, regarding the filtration accuracy of the filter in step 3_1, is filtered by conditions of 1, 3, 5, 7, and 1 respectively. As for the instrument, a deep type filter that uses a small pressure loss and can obtain a large flow rate is used. Fig. 8 is a graph showing the effect of filterless filter accuracy on the removal performance of coarse particles. The vertical axis indicates the number of coarse particles in the cerium oxide slurry, which is shown in the figure; the number of coarse particles in the rain treatment and the number of coarse particles after the filtration treatment. The straight line 29 indicates the change in the number of particles when the filtration precision is 1 μηη. , 91070-970718.doc •18· 1306115 Line 30 indicates the change in the number of particles when the filtration accuracy is 3 μηι, line 3 1 indicates the change in the number of particles when the filtration accuracy is 5 μπι, and the line 3 2 indicates the filtration accuracy. The change in the number of particles in the case of 7 μηι, the straight line 33 indicates the change in the number of particles in the case where the accuracy is 10 μιη. When the filtration accuracy is 5 μηι, 7 μηι, or 1 〇 μηΐ2, since the filtration accuracy is larger than the particle diameter of the coarse particles, the number of coarse particles after the filtration treatment hardly changes, and sufficient filtration performance cannot be obtained. In this case, when the filtration precision is 1 μηη or 3 μιη, the number of coarse particles after the filtration treatment is largely reduced. Next, regarding the processing flow rate of the filter in the step 3-1, the filtration is performed under the same conditions as described above. Figure 9 is a graph showing the effect of filter filtration accuracy on the processing flow rate. The vertical axis represents the processing flow rate of the filtration process, and the processing flow rate for each filtration accuracy is shown in the figure. Symbol 74 indicates the flow rate when the filtering accuracy is i μιη, symbol 75 indicates the flow rate when the filtering accuracy is 3, symbol % indicates the flow rate when the filtering accuracy is 5 μηη, and symbol 77 indicates that the filtering accuracy is 7 μπ! In the case of the flow rate, the symbol 78 indicates the flow rate when the filtration accuracy is 1 。. As can be seen from the figure, the smaller the filtration accuracy, the smaller the flow rate. In consideration of the actual manufacturing steps, if the flow rate is 2 liters/min or more, the utility can be practically used, so that the filtration accuracy is 1 μηι. Considering the removal performance of the coarse particles and the treatment flow rate, it is known that a filter having a filtration accuracy of 1 to 4 pm can be used. The treatment flow rate at this time becomes 2 to ι liter/min. 91070-970718.doc -19- 1306115 Secondly, based on the prior art, the sputum sputum slurry is prepared according to the present invention, and the sputum sputum slurry is prepared according to the prior art. Note: The i-th 仏μμ is called the embodiment!"))")")"""""""""" It is called "Oxidized Oxide 浓 产 t 卜 & & & & f f f f f f f f f f f f f ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) Example 1 was made according to the following procedure.
(a)將超純水置入至高剪壯 值調整為2。 ”政衣置中，添加鹽酸將PH (b)供給高剪切力，並且和人盗如|斗、& 芷且杈入軋相式氧化矽直至初期氧 化矽濃度成為5 〇重量。/。。 ⑷投入氣指式氧切後’對二氧切分散液供給高剪切 力2小時30分鐘。 (d) 為使氧化矽分散液之濃度成為49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丨小時。 (f) 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 度之氫氧化鉀水溶液中。 (g) 再者’使用過濾精度為3 μιη之深度型過濾器，除去 粗大粒子。 圖10係表示比較例1以及2、實施例1中所含之粗大粒子 91070-970718.doc 20- 1306115 數的圖表。縱 规抽表不粗大粒子數，橫軸表示粒子直徑。曲 線39表示實祐也丨， 4 1 ’曲線40表示比較例1，曲線41表示比較 Μ大口 減/h 列1之粗大粒子數與比較例1以及2相比大幅度 择 胃於粗大粒子數以及其他之物性值，表1中表示3種 乳化矽衆料之比較結果。 [表1 ] 中間粒子 粗大粒子數 粗大粒子數 直徑[mr(] (>0.5 μηι) (>1 μιη) [粒子/ [粒子/ 0.5 ml] 0.5 ml] 112 100,000 2,000 氧化硬濃度 [重量％] PH[—]黏度[cP](a) Put ultrapure water into the high shear value and adjust to 2. "The government clothes are centered, adding hydrochloric acid to supply PH (b) to high shear force, and colliding with people such as hopper, & 杈 杈 杈 轧 轧 轧 轧 轧 轧 轧 轧 轧 轧 轧 轧 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽(4) After the gas-indicated oxygen cutting, the high-shear force is supplied to the dioxate dispersion for 2 hours and 30 minutes. (d) In order to make the concentration of the cerium oxide dispersion to be 49% by weight, a small amount of ultrapure water is added continuously. High shear force was supplied for 30 minutes. (e) In order to make the cerium oxide concentration of the cerium oxide dispersion 40% by weight, ultrapure water was added and supplied with high shear force for a few hours. (f) For the oxidized mash of the final product The pH of the material was 11 and the concentration of cerium oxide was 25% by weight, and the cerium oxide dispersion was poured into an aqueous potassium hydroxide solution adjusted to the concentration of potassium hydroxide. (g) Further, 'the depth of the filter with a precision of 3 μm was used. The filter removes the coarse particles. Fig. 10 is a graph showing the numbers of the coarse particles 91070-970718.doc 20- 1306115 contained in Comparative Examples 1 and 2 and Example 1. The vertical gauge indicates that the number of coarse particles is not large, and the horizontal axis indicates Particle diameter. Curve 39 indicates that the real is also 丨, 4 1 'curve 40 indicates the ratio In Example 1, the curve 41 indicates that the number of coarse particles of the larger mouth drop/h column 1 was significantly larger than that of the comparative examples 1 and 2, and the number of coarse particles and other physical properties. Table 1 shows three kinds of emulsified cockroaches. Comparison results. [Table 1] Intermediate particles Large particles Number of coarse particles Number diameter [mr(] (>0.5 μηι) (>1 μιη) [Particles / [Particles / 0.5 ml] 0.5 ml] 112 100,000 2,000 Oxidized hard Concentration [% by weight] PH[-] viscosity [cP]
如表1所不，實施例1中儘管中間粒子直徑小 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係表不CMP裝置1〇〇之概要外觀圖。CMp裝置1〇〇由 研磨墊ιοί、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之矽晶圓壓接，並藉由與矽晶圓相對移動而 研磨石夕晶圓表面。 旋轉定盤部121係包含將研磨墊ι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1〇3的支持 910709707】8. doc -21 ^ 1306115 手段。藉由旋轉驅動機構103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、以及研磨塾1 〇 1之 · 種類等選擇適當的旋轉數。 ， 載體部122如圖1 2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i 〇丨與矽晶圓i 〇8壓接之狀 態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 籲 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 % 106保持矽晶圓108之外周部。旋轉驅動機構1〇7係介由 疑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1〇8一同以特定之旋轉數於垂直方向 軸線附近旋轉。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、以及研肇 磨墊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 ιοί以及矽晶圓108。载體部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。 漿料供給部123係包含噴嘴1〇9、漿料供給管11〇以及漿 料槽111之供給手段。 藉由泵等將儲留於漿料槽i丨丨之氧化矽漿料，流入漿料 91070-970718.doc •22- 1306115 供給管110内，並自設置於旋轉定盤部121之上部且大致中 央部之喷嘴109對於研磨墊101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1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 斤構成之再生手&。於修整時，藉由旋轉駆動機構113 使薄板112旋轉，且將研磨㈣！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1〇8之狀態下，漿料供 給部123供給氧切衆料。供給之氧切漿料浸透至研磨 墊101與矽晶圓〗08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。 (υ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121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㈣進行研磨處 理。 ⑺於研磨塾101半徑與石夕晶圓108半徑間的差相差不太 91070-970718.doc -23- 1306115 大時則（1)亦可，但於研磨墊101半徑大於矽晶圓9之粒子直 徑時，存在有研磨墊101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，除之旋轉定盤部 U1與載體部122之自轉以外，載體部122於旋轉定盤部 之半徑方向上來回移動。 (3) 除（1)之旋轉定盤部121與載體部ι22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。 (4) 與（2)相同’於研磨墊ι〇1半徑大於矽晶圓ι〇8半徑 日守’將半徑方向上來回移動與旋轉定盤部121之中心周圍 旋轉移動予以組合。例如，於旋轉定盤部丨2丨之中心周圍 有如描繪螺旋軌道般移動載體部1 22即可。 再者，旋轉定盤部121以及載體部122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$疋轉速度亦可相同，亦可不同。 ^正。卩124之修整時期，存在有於研磨處理丄或複數個石夕 晶圓後進行之情形、以及於研磨處理中進行之情形。修整 邛124之金剛石薄板112之半徑小於研磨墊之半徑之情 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12 1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日夺，如圖所 示挾住旋轉定盤部121之中心而配置於載體部丨22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。 作為被研磨物，使用TEOS晶圓，作為研磨墊1〇1，使用 91070-970718.doc 1306115 IC1400 K-Gro〇ve(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1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 μ m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。縱軸表示每丨個晶圓之劃痕數。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1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，可以其他各種 方式進行f 。因匕，前述之實施方式冑為所有重點之單 純例不’本發明之範圍係表示於申請專利範圍，並不限於籲 說明書本文中。再者，屬於f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 如上根據本發明，對於經調製之鹼性物質水溶液中，藉 由添加氣相式氧化發分散液，可獲得分散穩定性優良，且 凝聚粒子少之研磨用組合物。 又根據本發明’可有效供給高剪切力，並提高分散性。 91070-970718.doc •25- 1306115 精由添加少量水而可降低研 之黏度。 又根據本發明，藉由於^ 、 猎由於5小時以内終止混合而吁迅速降 低混合液之pH值，缩柄坤士、>丄 縮短以成虱相式氧化矽易凝聚之pH條 件的時間並可抑制凝聚產生。 根據本發明，於第2步驟中獲得之研磨用組合物因凝 ’故而藉由職處理可有效除去凝聚物。 【圖式簡單說明】As shown in Table 1, in Example 1, although the diameter of the intermediate particles was small, the concentration of cerium oxide was high, but the viscosity was lowered. Further, the cerium oxide wafer is actually polished using the cerium oxide slurry. Fig. 11 is a schematic external view showing a CMP apparatus. The CMp device 1 is composed of a polishing pad ιοί, a rotating platen portion 121, a carrier portion 122, a slurry supply portion 123, and a trimming portion 124. The polishing pad 101 is crimped to the wafer held by the carrier portion 122 of the CMp device 1 and is polished by the relative movement of the wafer. The rotary modulating portion 121 includes a fixed plate 102 for attaching and supporting the polishing pad 1 to the front surface of the fixed plate 102 by an adhesive tape or the like, and a rotary drive connected via a rotating shaft provided on the lower surface side of the fixed plate 102. Agency 1〇3 support 910709707] 8. doc -21 ^ 1306115 means. The rotational driving force generated by the rotary drive mechanism 103 is transmitted to the fixed plate 102 by the rotary shaft. The fixed disk 102 rotates in the vicinity of the vertical axis with a specific number of rotations together with the polishing pad 1〇1. The number of rotations can be freely set, and the appropriate number of rotations can be selected by the type of the wafer to be polished or the type of the film, and the type of the polishing 塾1 〇 1 . As shown in the cross-sectional view of FIG. 12, the carrier portion 122 includes a carrier body 4, a support member 105, a retainer ring 1 〇6, and a rotary drive mechanism 丨〇7, and holds the object to be polished, that is, the wafer 1 〇8, a means for holding the rotation of the polishing pad i 〇丨 and the 矽 wafer i 〇 8 in a state of being pressed. The attachment of the carrier body 1〇4 of the wafer 1〇8 is such that the support material 105 is wetted and sucked by the surface tension of the water. Further, in order to prevent the wafer 1 to 8 from falling off during the polishing process, the outer circumference of the wafer 108 is held by the retainer % 106. The rotary drive mechanism 1〇7 is connected to the upper side of the carrier body 1〇4 via the suspected rotating shaft, and the rotational driving force generated by the rotary drive mechanism 107 is transmitted to the carrier body 1〇4 through the rotary shaft, and the carrier body 104 and the crucible The wafers 1〇8 rotate together in a vicinity of the vertical axis with a specific number of rotations. The number of rotations can be freely set, and similarly to the rotation and fixing portion 121, an appropriate number of rotations can be selected by the type of the wafer to be polished, the type of the film, and the type of the polishing pad 101. Further, the carrier portion 122 is attached to the direction of the rotary fixed portion 121, is pressed vertically downward, and is pressed against the polishing pad ιοί and the wafer 108. The pressurization of the carrier portion 122 can be applied by the rotary drive mechanism 107, and other pressurizing mechanisms can also be used. The slurry supply unit 123 includes supply means for the nozzle 1〇9, the slurry supply tube 11〇, and the slurry tank 111. The cerium oxide slurry stored in the slurry tank i by the pump or the like flows into the supply pipe 110 of the slurry 91070-970718.doc • 22-1306115, and is disposed above the rotary fixing plate portion 121 and substantially The nozzle 109 at the center portion is supplied to the surface of the polishing pad 101 at a specific flow rate. As the cerium oxide slurry to be supplied, the slurry of Example 1 and Comparative Examples 1 and 2 was used. With the progress of the polishing, the polishing dust or the abrasive grains are clogged in the fine pores in the vicinity of the polishing surface of the polishing pad 1〇1, and the polishing properties such as the polishing rate are lowered. The trimming portion 124 is a regenerative hand & which is composed of a thin plate 112 to which an industrial diamond particle is attached, which is a regulator, and a rotary drive mechanism which is connected to the thin plate 112 via a rotating shaft. At the time of trimming, the thin plate 112 is rotated by the rotary swaying mechanism 113, and the grinding is performed (four)! The abrasive surface is in contact with the diamond particles, and the clogging portion is removed, thereby regenerating the polishing property of the polishing pad 1〇1. With respect to the operation of each portion during the polishing process, the carrier portion 122 is vertically pressed downward, and in the state where the polishing pad 101 and the wafer 1B are crimped, the slurry supply portion 123 supplies the oxygen cut. The supplied oxygen cutting slurry is impregnated between the polishing pad 101 and the crucible wafer 08, and rotates and relatively moves the rotating platen portion 121 and the carrier portion 122' by mechanical action of the medium and the mechanical action of the abrasive particles. High-precision grinding of the surface of the wafer 1 〇8. There are various ways in which the relative movement of the rotary platen portion 121 and the carrier portion 122 are as follows. (As shown in the drawing, the carrier portion 122 is disposed such that the center of the carrier portion 122 is located at a position 1/2 of the radial center of the rotation of the rotary disk portion 121 and only the rotary disk portion 121 and the carrier portion 122 are rotated. (4) Grinding treatment. (7) The difference between the radius of the grinding crucible 101 and the radius of the silicon wafer 108 is not too different. 91070-970718.doc -23- 1306115 is large (1) is also possible, but the radius of the polishing pad 101 is larger than When the particle diameter of the wafer 9 is small, there is a portion where the surface of the polishing pad 101 is not in contact with the wafer 1 8 , so that the entire surface of the polishing pad 101 can be used, except that the disk portion U1 and the carrier portion 122 are rotated. In addition to the rotation, the carrier portion 122 moves back and forth in the radial direction of the rotary fixed portion. (3) The carrier portion 122 is at the center of the rotary fixed portion 121 except for the rotation of the rotary fixed portion 121 and the carrier portion ι22 of (1) (4) Same as (2) 'The radius of the polishing pad ι〇1 is larger than the radius of the 矽104 〇8 radius. The movement is repeated in the radial direction and the rotation around the center of the rotating platen 121. For example, around the center of the rotating platen 丨2丨The carrier portion 1 22 may be moved like a spiral track. Further, the rotation direction of the rotation plate portion 121 and the carrier portion 122 may be the same or different. Further, the rotation plate portion 121 and the carrier portion 122 are rotated by $ The twisting speed can be the same or different. ^正. The finishing period of 卩124 exists in the case of grinding treatment or multiple stone wafers, and in the grinding process. The radius of the diamond thin plate 112 is much smaller than the radius of the polishing pad. Therefore, when the polishing process is performed after the polishing process, the relative movement of the rotary disk portion 12 1 and the carrier portion 122 is performed (2) and ( 4) It is sufficient to carry out the same process in the polishing process, as shown in the figure, the center of the rotary fixed disk unit 121 is placed on the opposite side of the carrier portion 22, and the relative movement is performed (2). The polishing process may be performed in the same manner as in the above CMP apparatus. As the object to be polished, a TEOS wafer is used as the polishing pad 1〇1, and 91070-970718.doc 1306115 IC1400 K-Gro〇ve is used. R〇 Del Nitta Co., Ltd.) The rotation speed of the rotary platen unit 121 is set to 60 rpm' and the cerium oxide slurry is supplied at a speed of 1 〇〇ml/min. After 1 minute of grinding treatment, it is manufactured by Hitachi Electronic Technology Co., Ltd. The wafer surface inspection device (LS6600) calculates the number of scratches and marks on the surface of the wafer (the size is 0, 2 μm or more). Fig. 13 shows the use of the polishing process of Example 1 and Comparative Examples 1 and 2. The graph of the fruit indicates that the vertical axis represents the number of scratches per wafer. The polishing treatment was performed three times on Example i and Comparative Examples 1 and 2, respectively. The number of scratches in Comparative Example 1 was 261 to 399 (average 322), and the number of scratches in Comparative Example 2 was 103 to 154 (average 123), and the number of scratches in Example 1 was greatly reduced to 28 to 63 (average 40) ). Thus, the cerium oxide slurry prepared by the present invention has high dispersibility and a small number of coarse aggregated particles, so that the number of scratches on the surface of the wafer can be reduced in the polishing process. The present invention can be carried out in various other ways without departing from its spirit or essential characteristics. Because the foregoing embodiments are the only ones of all the advantages, the scope of the present invention is not limited to the scope of the claims. Furthermore, variations or modifications that fall within the scope of the invention are within the scope of the invention. Industrial Applicability According to the present invention, by adding a gas phase oxidized hair dispersion liquid to an aqueous solution of a prepared alkaline substance, a polishing composition having excellent dispersion stability and a small amount of aggregated particles can be obtained. Further, according to the present invention, high shear force can be efficiently supplied and the dispersibility can be improved. 91070-970718.doc •25- 1306115 The viscosity can be reduced by adding a small amount of water. According to the present invention, since the pH of the mixed solution is rapidly lowered due to termination of mixing within 5 hours, the shrinkage of the mixture is shortened to a pH condition of the 虱 矽 矽 矽 并 并 并Can inhibit the formation of agglomeration. According to the present invention, the polishing composition obtained in the second step can be effectively removed by coagulating treatment. [Simple description of the map]
圖1係本發明一實施樣態之流程圖。 圖2係表示灣對於凝聚粒子成長率之影響圖表。 久表示氧化矽分散液的初期氧化矽濃度對於氧化矽 聚料之粒度分佈之影響圖表。 圖4係表示氧切濃度對於氧切裝料中之粗大粒子數 之影響圖表。 圖5係表不混合條件對於氧化石夕聚料之粒度分佈之影響 圖表。1 is a flow chart of an embodiment of the present invention. Figure 2 is a graph showing the effect of the Bay on the growth rate of aggregated particles. It shows for a long time the effect of the initial cerium oxide concentration of the cerium oxide dispersion on the particle size distribution of the cerium oxide polymer. Figure 4 is a graph showing the effect of oxygen cut concentration on the number of coarse particles in the oxygen cut charge. Figure 5 is a graph showing the effect of no mixing conditions on the particle size distribution of the oxidized oxide aggregate.
圖6係表示氧切分散液投人時間對於氧切漿料之粒 度分佈之影響圖表。 圖7係表示氧化矽分散液之投入速度對於混合液之p Η值 之影響圖表。 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。 ° y、表示過;慮器過遽精度對於處理流速之影塑圖。 圖10係表示比較例i以及2、f施例…粗大粒子數的 91070-9707l8.doc -26· 1306115 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。 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 果圖。 【主要元件符號說明】 100 CMP裝置 101 研磨塾 102 定盤 103, 107, 113 旋轉驅動機構 104 載體本體 105 支撐材 106 護圈環 108 石夕晶圓 109 喷嘴 110 漿料供給管 111 漿料槽 112 薄板 121 旋轉定盤部 122 載體部 123 漿料供給部 124 修整部 91070-970718.doc -27-Fig. 6 is a graph showing the effect of the oxygen-cut dispersion on the particle size distribution of the oxygen-cut slurry. Fig. 7 is a graph showing the effect of the input speed of the cerium oxide dispersion on the p Η value of the mixed liquid. Fig. 8 is a graph showing the effect of filter filtration accuracy on the removal performance of coarse particles. ° y, expressed too; the accuracy of the device over the 对于 is the shadow of the processing flow rate. Fig. 10 is a graph showing the comparative examples i and 2, the f example, the number of coarse particles, 91070-9707l8.doc -26·1306115. FIG. 11 is a schematic external view showing the CMP apparatus 100. Figure 12 is a cross-sectional view of the carrier portion 122. Fig. 1 is a graph showing the results of polishing treatment using Example 1 and Comparative Examples 1 and 2. [Description of main components] 100 CMP apparatus 101 Grinding 塾102 Fixed discs 103, 107, 113 Rotary drive mechanism 104 Carrier body 105 Support material 106 Retaining ring 108 Shixi wafer 109 Nozzle 110 Slurry supply pipe 111 Slurry tank 112 Thin plate 121 Rotating platen portion 122 Carrier portion 123 Slurry supply portion 124 Trimming portion 91070-970718.doc -27-