200923079 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種清洗液及其在化學機械拋光後晶片清洗之 應用。 、 【先前技術】 f 在半導體製程中’化學機械拋光(CMP)之方式時常被用以使 晶片，表面平整化。在研磨漿料並拋光晶片之後，在晶片表面會 產生許多殘留物，例如研磨顆粒、研磨漿料中的化學成分及拋光 水料的反應生成物。這些殘留的污染物必須在進入到下一個 體製程之步驟前被清洗乾淨，否卿會嚴重影響賴之製程以及 在罐過⑽嘯，騎使用一 i機環：染該清洗液中所使用的氨4 洗液因二種應用於化學機械抛光後晶片清洗之清 【發明内容】 之目的疋為了解決上述問題，而提供—種清洗液。 物和$發明提出之清洗液，含有至少—氧化劑、至少-胍類化合 200923079 在所月中，胍類化合物係具有去除殘餘研磨顆粒之作用。 類化合物中，較佳的選擇有:胍、碳酸胍、= 鹽、氨基胍触鹽、氨基胍鹽酸或碳酸氫 合物的較佳含量_百分比〇；=板財至於胍類化 f甲it發9种’減狀健選擇為魏化氫、魏化脲、過 或過氧乙酸。至於氧化劑之較佳含量為品質百分比01_200923079 IX. INSTRUCTIONS: TECHNICAL FIELD OF THE INVENTION The present invention relates to a cleaning fluid and its use in wafer cleaning after chemical mechanical polishing. [Prior Art] f In the semiconductor process, the method of chemical mechanical polishing (CMP) is often used to flatten the surface of the wafer. After the slurry is polished and the wafer is polished, a number of residues are generated on the surface of the wafer, such as abrasive particles, chemical components in the abrasive slurry, and reaction products of the polishing water. These residual contaminants must be cleaned before entering the next process. If there is a serious impact on the process and the cans (10), use an i-ring: the dye used in the cleaning solution. The purpose of the invention is to provide a cleaning liquid for the purpose of solving the above problems, because the ammonia 4 washing liquid is applied to the cleaning of the wafer after chemical mechanical polishing. The cleaning solution proposed by the invention and the invention contains at least an oxidizing agent and at least a hydrazine compound. 200923079 In the month, the quinone compound has the function of removing residual abrasive particles. Among the compounds, preferred choices are: hydrazine, cesium carbonate, = salt, amino guanidine salt, aminoguanidine hydrochloride or hydrogen carbonate, the preferred content _ percentage 〇; = 财 至 胍 胍 胍 f The nine types of 'subtractive health' are selected as Wei hydrogen, Wei urea, or peroxyacetic acid. As for the preferred content of the oxidant, the quality percentage is 01_
之藤中，清洗液之PH值可以介於PH 7调12，而較佳 機酸間。在實際應用中，可視需要採用無 機I寺吊規ΡΗ調節劑來調節該清洗液至所需的ρΗ值。 :艮，本發明之m在製備時*加人水胍類化合物後， ΐΐΐΐ均句’並視需要採用無機酸等常規pH調節劑調節清洗 =至所而的pH值。該清洗液在使用之前只需加入氧化劑混合均 本發明之另一目的在於將該清洗液應用於經過化學機械拋光 後之晶片清洗過程。該晶片之種類可以是多晶矽、單晶 二 化石夕等非金屬晶片。 本發明所提出之清洗液可去除在經過化學機械拋光後之晶片 表面上所殘留之研磨顆粒及化學物質。並且由於該清洗液之金屬 離子含量低且無氣味，因此可以減少金屬離子所造成之污染。 關於本發明之優點與精神可以藉由以下的發明詳述得到進一 步的瞭解。 【實施方式】 下面通過實施例的方式進一步說明本發明，但是並不因此將 200923079 本發明限制在下列所述的實施例範圍之中。 實施例1-Π 表1顯示了用於清洗液實施例1〜13的配方，水為餘量。 表中所給各成分及其含量，先加入水和胍類化合物 ’並加以攪拌 句二勻’之後採用石鑛調節到使用者所需㈣PH值，使用前只需 在該清洗液加入氧化劑混合均勻即可。 實施例 含量 wt% 8 1 2.5 5 表1清洗蜂實施例1〜13 胍類化合物 胍 10 氨基胍In the vine, the pH of the cleaning solution can be adjusted from pH 7 to 12, and is preferably between acid and acid. In practical applications, an inorganic I sling regulator can be used to adjust the cleaning solution to the desired value of ρ 可视. : 艮, the m of the present invention is prepared by adding a human hydrazine compound at the time of preparation, and adjusting the pH to the desired pH value by using a conventional pH adjusting agent such as a mineral acid as needed. The cleaning solution is simply added with an oxidizing agent prior to use. Another object of the invention is to apply the cleaning solution to a wafer cleaning process after chemical mechanical polishing. The type of the wafer may be a non-metal wafer such as polycrystalline germanium or single crystal diamond. The cleaning solution proposed by the present invention can remove abrasive particles and chemicals remaining on the surface of the wafer after chemical mechanical polishing. Moreover, since the cleaning liquid has a low metal ion content and is odorless, contamination by metal ions can be reduced. The advantages and spirit of the present invention will be further understood from the following detailed description of the invention. [Embodiment] The present invention is further illustrated by the following examples, but the invention is not limited to the scope of the embodiments described below. Example 1 - Π Table 1 shows the formulations used in the cleaning solutions of Examples 1 to 13, with water being the balance. The ingredients and their contents in the table, first add water and terpenoids 'and stir them evenly', then use the stone ore to adjust to the user's required (four) PH value, just add the oxidant and evenly mix in the cleaning solution before use. Just fine. EXAMPLES Content wt% 8 1 2.5 5 Table 1 Cleaning bees Examples 1 to 13 Terpenoids 胍 10 Aminoguanidine
0.1 -—· 10 0.5 4 3 2 硝酸胍 氨基胍 硫酸胍 碳酸胍 具體物質 磷酸氫二胍 氨基胍磺酸鹽 碳酸胍 氨基胍破酸氫鹽 氨基胍鹽酸鹽 氧化劑 含量 wt% 具體物質 pH值 1 過氧化氫 7 0.5 過氧化氫 8 2 過氧化氫 10 3 過氧化氩 11 0.1 過氧化氫 12 2 過氧甲酸 10 5 過氧化脲 10 2 過氧乙酸 9 6 過氧化氫 9 1 過氧化氫 8 7 200923079 11 2 氨基胍硝酸鹽 1 過氧化氫 8 12 0.01 乙酸胍 10 過氧化氫 —---- 7 13 5 碳酸脈 1 過氧化氫 ^—-- 2 過氧化脲 9 L—---- 效果實施例1 . 分別採用去離子水和實施例3的清洗液，對於經過化學機械 拋光後的多晶矽晶片表面進行刷洗。在本實施例中，使用的宁刷 n 為聚乙烯醇(PVA)滚刷，刷洗時間為lmin，滚刷轉速為1〇〇φ=， 清洗液流量為500ml/min。用去離子水清洗後的晶片表面，如圖i 和2所示；用清洗液清洗後的晶片表面，如圖3所示。 如圖1至圖3所示，根據本發明之清洗液對於多晶矽曰片拋 光後表面所殘留之研磨顆粒及化學物質具有良好的清洗能I。而 且在清洗過程中，該清洗液之金屬離子含量低且無氣味， 以減少金屬離子所造成之污染。 效果實施例2 t 分別採用去離子水和實施例7的清洗液，對經過化學機械拋 光後的二氧化矽晶片表面進行刷洗，在此實施例中’所使用的滾 刷為聚乙稀醇(PVA)滾刷’刷洗時間，滾刷轉速為1〇叫皿， 清洗液流量為500ml/min。用去離子水清洗後的晶片表面，如圖4 所示。用清洗液清洗後的晶片表面，如圖5所示。 如圖4及圖5所示，根據本發明之清洗液對於二氧化石夕晶片 經過撤光後在表面所殘留之研磨顆粒和化學物質具有良好的 '青、、先 能力。而且在清洗過程中，根據本發明之清洗液的金屬離子含量 低且無氣味，因此可以減少金屬離子所造成之污染。 200923079 效果實施例3 矽ριίϋϊΐΐ離子水和實施例9的清洗液，對有多曰曰矽/二氣化 中:使用學機難光後的表面進行刷洗，在本實施例 片表面，如圖3 為5Gi)ml/min。用去離子水清洗後的晶 示。 不’用清洗液清洗後的晶片表面，如圖7所 晶片婉=拋’根據本發明之清洗液對於多晶石夕/二氧化石夕 的清;能力tii=;r化學物質具有良好 本發明所使用的原料和試劑均是市售所得。 發明具體實施例之詳述，係希望能更加清楚描述本 ==加，限制。相反地，其目的=能== tHi·生的女排於本發明所欲申請之專利範圍的範脅内。因 ί的ir所ΐ請之專利範_範嘴應該根據上述的說明作最寬 廣的轉，贿使其涵蓋触可㈣轉叹射目等性的安排。 200923079 [圖式簡單說明】 圖一為使用去離子水清洗後的多晶梦晶片表面的SJBM圖， 其中之白色斑點為晶片表面殘留的研磨顆粒。 ° 圖二為使用去離子水清洗後的多晶石夕晶片表面的SEM圖， 其中之白色斑跡為晶片表面殘留的化學物質。 θ 圖三為使用實施例3的清洗液清洗之後多晶矽晶片矣 SEM圖。 曰々衣曲的 SEM 面的 圖四為使用去離子水清洗後的二氧化矽晶片表面的 圖’其中之白色斑點為晶片表面殘留物。 SEM圖圖五為細實細7崎洗崎洗後的二氧切晶片表 圖六為使用去離子水清洗後的有圖案的多晶足 表面的瞻圖，其中之職為W表面殘〜祕石夕晶片 化心清洗液清洗後的有圖案的多晶-二氧 【主要元件符號說明】 無 100.1 --· 10 0.5 4 3 2 cerium nitrate amino sulfonium sulphate strontium carbonate specific substance hydrogen phosphate dihydrazone amino sulfonium sulfonate hydrazine amino hydrazine acid hydrogen salt amino hydrazine hydrochloride oxidant content wt% specific substance pH value 1 Hydrogen peroxide 7 0.5 Hydrogen peroxide 8 2 Hydrogen peroxide 10 3 Argon peroxide 11 0.1 Hydrogen peroxide 12 2 Peroxycarboxylic acid 10 5 Peruret peroxide 10 2 Peracetic acid 9 6 Hydrogen peroxide 9 1 Hydrogen peroxide 8 7 200923079 11 2 Aminoguanidine nitrate 1 Hydrogen peroxide 8 12 0.01 Barium acetate 10 Hydrogen peroxide ----- 7 13 5 Carbonic acid pulse 1 Hydrogen peroxide ^--- 2 Urea peroxide 9 L—---- Effect Example 1. The surface of the polycrystalline germanium wafer after chemical mechanical polishing was brushed using deionized water and the cleaning solution of Example 3, respectively. In the present embodiment, the N-brush n used is a polyvinyl alcohol (PVA) roller brush, the brushing time is 1 min, the rolling brush speed is 1 〇〇 φ =, and the cleaning liquid flow rate is 500 ml/min. The surface of the wafer after washing with deionized water, as shown in Figures i and 2; the surface of the wafer after cleaning with a cleaning solution, as shown in Figure 3. As shown in Figs. 1 to 3, the cleaning liquid according to the present invention has a good cleaning energy I for the abrasive particles and chemicals remaining on the surface of the polycrystalline silicon wafer after polishing. Moreover, during the cleaning process, the cleaning solution has a low metal ion content and is odorless to reduce the contamination caused by metal ions. Effect Example 2 t The surface of the chemically polished cerium oxide wafer was brushed with deionized water and the cleaning liquid of Example 7, respectively. In this embodiment, the roller brush used was polyethylene glycol ( PVA) Roller brushing time, the brushing speed is 1 〇, and the cleaning fluid flow rate is 500ml/min. The surface of the wafer after washing with deionized water is shown in Figure 4. The surface of the wafer after cleaning with a cleaning solution is shown in FIG. As shown in Fig. 4 and Fig. 5, the cleaning liquid according to the present invention has a good 'green' ability for the abrasive particles and chemicals remaining on the surface after the removal of the silica dioxide wafer. Further, in the cleaning process, the cleaning liquid according to the present invention has a low metal ion content and is odorless, so that contamination by metal ions can be reduced. 200923079 Effect Example 3 矽ριίϋϊΐΐ ion water and the cleaning solution of Example 9, in the case of multi-twist/two gasification: the surface after the use of the machine is difficult to light, on the surface of the sheet of the embodiment, as shown in FIG. 5Gi) ml/min. Crystallized after washing with deionized water. The surface of the wafer after cleaning with the cleaning solution, as shown in Fig. 7, the wafer is 抛 = throwing the cleaning liquid according to the present invention for the polycrystalline stone / sulphur dioxide eve; the ability tii =; r chemical has good the present invention The materials and reagents used are all commercially available. The details of the specific embodiments of the invention are intended to more clearly describe this == plus, limit. On the contrary, the purpose is to == tHi·the female volleyball is within the scope of the patent scope of the invention to be applied for. Because of the ί ir, the patent _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 200923079 [Simple diagram of the drawing] Figure 1 is a SJBM diagram of the surface of a polycrystalline dream wafer after washing with deionized water, wherein the white spots are abrasive particles remaining on the surface of the wafer. ° Figure 2 is an SEM image of the surface of a polycrystalline silicon wafer after washing with deionized water, where the white stain is a chemical remaining on the surface of the wafer. θ Figure 3 is an SEM image of a polycrystalline germanium wafer after cleaning using the cleaning solution of Example 3. Figure 4 of the SEM surface of the koji shows the surface of the cerium oxide wafer after washing with deionized water. The white spots therein are wafer surface residues. The SEM image is shown in Figure 5. The surface of the diced wafer after washing and washing is shown in Figure 6. Figure 6 is a schematic view of the patterned polycrystalline foot surface after washing with deionized water. Patterned polycrystalline-diox after cleaning of Shixi wafer core cleaning solution [Main component symbol description] No 10