508642 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（ 發明領域： 本發明係有關於相移式光罩的清洗製程，特別是有關 於去除相移式光罩中高分子膠的清洗製程。 發明背景： 改善晶圓微影製程之解析度的方法之一係利用相移式 (Phase Shifting)的微影製程，此相移式之微影製程係在習 知之光罩上添加部分相移層（Shifter layer)而形成相移式光 罩（Phase Shifting Mask)，藉著這層相移層在曝光時所衍生 的正反相干涉，可使曝光機投射在晶圓上的影像圖案有較 佳的解析度。其中，鉬矽氮氧化物（MosiON)係為通常用來 做為半調相移層的材料之一 β 習知在製作並清洗完相移式光罩後，會在相移式光罩 上加入一層光罩護膜（Pellicle)，以防止微塵粒子沾附在圖 案區中，而造成微影製程的缺陷，第1圖所繪示為一般具 有光罩護膜之相移式光罩示意圖。請參照第1圖，相移式 光罩10的主體係由平坦且透明的玻璃所構成，而製造積體 電路元件所需的圖案則是在玻璃表面附上一層厚度約數百 入的銷矽氮氧化物以及圖案外的鉻膜來構成。相移式光罩 10係具有非圖案區12與圖案區14,其中非圖案區12通常 本紙張尺度適用中關家標準（CNS)A4規 x 297公釐） --------^--------訂------—--線41^* (請先閱讀背面之注意事項再填寫本頁) 508642 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（） 係由鉻（Cr)或氧化鉻（CrO)薄膜所構成，而圖案區14係利用 玻璃（亦即石英材質）所形成的石英透明區1 6，以及相移層 1 6(MoSiON)所構成。另外，光罩護膜2〇係為鑲了塑膠框 的透明片，用於覆蓋在相移式光罩1 〇上，特別是圖案區i 4 上’並通常與相移式光罩1 〇保持一短距離，並利用黏膠以 將光罩護膜20裝置在相移式光罩上。 在光罩要出貨或者進行微影製程之前，會先進行一次 掃瞒動作以確認光罩上的圖案並無錯誤，如有缺陷（Defect) 存在，則必須進行再清洗與再修補的步驟。進行再清洗步 驟之前，會先將光罩上光罩護膜去除，第2圖所繪示為一 般去除光罩護膜之相移式光罩示意圖。請參照第2圖，其 中’去除光罩護膜後的相移式光罩丨〇係具有非圖案區！ 2 與圖案區14。接著，進行再清洗製程，第3圖所繪示為習 知袓移式光罩清洗製程流程圖。 請參照第3圖，相移式光罩的清洗製程，係依序利用 第一清洗步驟120、第二清洗步驟122、第三清洗步驟124 與第四清洗步驟126進行清洗。其中第一清洗步驟120所 具有的清洗溶液係為硫酸與過氧化氫溶液（H2S〇4/ H2〇2 ;508642 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (Field of the invention: The present invention relates to the cleaning process of phase-shifting photomasks, and in particular to the cleaning of removing polymer glue in phase-shifting photomasks Background of the Invention: One of the methods to improve the resolution of wafer lithography is to use a phase-shifting lithography process. This phase-shift lithography process is to add a part of the phase to a conventional mask. A phase shift mask is formed by shifting the layer. The positive and negative phase interference derived from this phase shifting layer during exposure can make the image pattern projected on the wafer by the exposure machine. Better resolution. Among them, MoSiON is one of the materials commonly used as a half-phase-shifting layer. It is known that after the phase-shifting photomask is manufactured and cleaned, it will be in the phase. A layer of mask film (Pellicle) is added to the movable mask to prevent dust particles from adhering to the pattern area, which causes defects in the lithography process. The phase shift shown in Figure 1 is generally a mask film Schematic diagram of the photomask. Please refer to In Figure 1, the main system of the phase shift mask 10 is composed of flat and transparent glass, and the pattern required for manufacturing integrated circuit elements is to attach a layer of pin silicon oxynitride with a thickness of about several hundred on the glass surface. And a chrome film outside the pattern. The phase-shifting mask 10 has a non-patterned area 12 and a patterned area 14, of which the non-patterned area 12 usually applies the Zhongguanjia Standard (CNS) A4 rule x 297 mm for this paper size) -------- ^ -------- Order ---------- Line 41 ^ * (Please read the notes on the back before filling this page) 508642 Intellectual Property Bureau of the Ministry of Economic Affairs Printed by employees' consumer cooperatives A7 B7 V. Description of the invention () is made of chromium (Cr) or chromium oxide (CrO) film, and the pattern area 14 is a quartz transparent area formed by glass (that is, quartz material) 1 6 And a phase shift layer 16 (MoSiON). In addition, the mask protective film 20 is a transparent sheet inlaid with a plastic frame, and is used to cover the phase-shifting photomask 10, especially the pattern area i4 ', and is usually maintained with the phase-shifting photomask 10. A short distance, and the adhesive is used to mount the photomask 20 on the phase shift photomask. Before the reticle is shipped or the lithography process is performed, a sweep operation is performed to confirm that the pattern on the reticle is free of errors. If a defect exists, it must be cleaned and repaired. Before performing the re-cleaning step, the photomask on the photomask is removed. Figure 2 shows a schematic diagram of a phase-shift photomask with the photomask removed in general. Please refer to FIG. 2, in which the phase-shifting photomask after removing the photomask has a non-patterned area! 2 and pattern area 14. Next, a re-cleaning process is performed, and FIG. 3 shows a flowchart of a conventional transfer mask cleaning process. Referring to FIG. 3, the cleaning process of the phase-shifting photomask is sequentially cleaned by using the first cleaning step 120, the second cleaning step 122, the third cleaning step 124, and the fourth cleaning step 126. Wherein, the cleaning solution of the first cleaning step 120 is a sulfuric acid and hydrogen peroxide solution (H2S〇4 / H2〇2;
Sulfuric Acid-Hydrogen Peroxide Mixture ; SPM)，而第二 清洗步驟1 24所具有的清洗溶液係為氫氧化銨與過氧化氫 之水 /谷液（NH4OH/H2O2/H2O; Ammonium Hydrogen Peroxide 本紙張又度適用中國國家標準（CNS)A4規格（210 X 297公餐） l·------------^--------^0, (請先閱讀背面之注意事項再填寫本頁) 508642 經濟部智慧財產局員工消費合作社印製 A7 B7 — 五、發明說明（）Sulfuric Acid-Hydrogen Peroxide Mixture; SPM), and the second cleaning step 1 24 has a cleaning solution of ammonium hydroxide and hydrogen peroxide water / valley (NH4OH / H2O2 / H2O; Ammonium Hydrogen Peroxide) Applicable to China National Standard (CNS) A4 specification (210 X 297 meals) l · ------------ ^ -------- ^ 0, (Please read the precautions on the back first (Fill in this page again) 508642 Printed by the Consumers' Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 — V. Description of Invention ()
Mixture，APM，亦稱SCI或HA)，另外介於第一清洗步驟 120與第三清洗步驟124之間的第二清洗步驟ι22，以及第 三清洗步驟1 24之後的第四清洗步驟丨26所具有的清洗溶 液係為超純水（D.I· Water;亦稱去離子水），可去除殘留的 清洗溶液。如此’便可完成相移式光罩之清洗製程。 習知清洗製程係依序利用硫酸與過氧化氫溶液 (SPM)、超純水、氫氧化銨與過氧化氫之水溶液（SCi)、與 超純水四種清洗溶液。其中，SPM係用來去除較大的有機 分子，而SCI係用來去除較小的有機分子與微粒子而超純 水的作用係用來去除先單殘留的清洗溶液。但是，·一般光 罩護膜所使用在相移式光罩上的黏膠係為酯類結構， (RCOOR)x，例如聚丙烯酸酯的高分子結構，當光罩浸入 SPM的清洗槽中，（RCOOR)x會水解形成可流動但不溶於水 的膠態物質，（RCOOH)x。因此（RCO〇H)x在相移式光罩之 清洗製程中，有可能流入相移層區，而與鉬矽氧氣化物 (MoSiON)上的氮原子（N)起化學反應，形成無法去除的污染 物，（RCOO)NOSiMo，所以造成光罩圖案上的缺陷與光罩 的報廢。 發明目的及概述： 鑒於上述之習知清洗製程之缺點，因此，本發明的目 本紙張尺度適用中國國家標準（CNSM4規格（210 X 297公釐） l·----·---7---费--------訂 -------:線· (請先閱讀背面之注意事項再填寫本頁) 5ι A7 五、發明說明（） 、係提供一種相移式光罩的清洗製程，可使原裝置光罩護 膜所使用的黏膠去除完全，而減少微影製程的缺陷與光罩 的報廢。 本發明相移式光罩之清洗製程包括：使該相移式光罩 係依序利用下列清洗溶液來洗淨，氫氧化銨與過氧化氫之 水备液（SC 1 )、超純水、硫酸與過氧化氫溶液、超純水、氫 氧化錄與過氧化氫之水溶液；以及超純水。 本發明相移式光罩之清洗製程係使用在相移式光罩之 正常清洗製程之前，即在相移式光罩之正常清洗製程之 前，先利用氫氧化錄與過氧化氫之水溶液（SCI)來清洗相 式光罩，接著利用超純水來清洗，隨後，便可進行一 般相 宜光罩之清洗製程。 上述之氫氧化銨與過氧化氫之水溶液（SCI)中，水 卜 氧化銨與過氧化氫的體積比為1··Χ:Υ，其中父後， 氣 饰小於等 於卜Υ係小於等於1，並浸泡s C 1溶液約1分鐘至5八梦 較佳係浸泡約2分鐘。 I-----；---Τ-----------訂· (請先閱讀背面之注意事項再填寫本頁} 線 經濟部智慧財產局員工消費合作社印製 罩， 光度 式確 移精 相的 將程 有製 具影 但微。 不高本 程提成 製並廢 洗，報 清點的 之優成 罩的造 光淨所 式乾損 移除污 相去罩 明物光 發染因 本污低 的減 上更 本紙張尺度適用中國國家標準（CNS)A4規格（21〇x 29/公餐） 508642 A? B7 意 五、發明說明（ 圖式簡單説明： 本發明的較佳實施例將於往後之說明文字中辅以下列 圖形做更詳細的闡述’其中·· 第1圖所繪示為一般具有光罩護膜之相移式光罩示 圖 第2圖所繪示為一般去除光罩護膜之相移式光罩示意 圖 第3圖所繪示為習知相移式光罩清洗製程流程圖；以 I — — — — — — — — ! — ! ' t I 請先閱讀背面之注意亊項再填寫本頁) 及 第4圖所繪示為本發明相移式光罩清洗製程流程圖 訂· 經濟部智慧財產局員工消費合作社印製 圖號對照説明： 10 光罩 12 非圖案區 14 圖案區 16 石英透明區 18 相移層 20 光罩護膜 120 第一清洗步驟 122 第二清洗步驟 124 第三清洗步驟 126 第四清洗步驟 210 第一清洗步驟 212 第二清洗步驟 220 第三清洗步驟 222 第四清洗步驟 4 本紙張尺度適用中國國家標準（CNS)A4規格（210x297公餐） 508642 五、發明說明（） 224 第五清洗步 驟 226 第六清洗步驟 經濟部智慧財產局員工消費合作社印製 發明詳細說明： 鑒於上述之習知清洗製程並無法將相移式光罩中殘留 光罩護膜的黏膠去除，並在清洗製程中流入相移層，而和 Mo Si ON進行反應，如此一來，黏膠的殘留物因此留在光 罩的圖案區中，而無法利用任何清洗製程來去除，不僅造 成晶圓微影製程的缺陷，更可能造成光罩的毁損報廢。 因此，本發明的目的係提供一種相移式光罩的清洗製 程，可使原裝置光罩護膜所使用的黏膠去除完全，而不造 成任何殘留現象。帛4圖輯示為本發明光罩清洗製程= 程圖》請參照第4 ® ’將相移式光軍係依序利用第一清洗 步驟21〇、第二清洗步驟212、第三清洗步驟22〇、第四清 洗步驟222、第五清洗步驟224、盥 ，、弟/、π洗步驟226進行 清洗，以完成相移式光罩的清洗製程。其中，第一清洗步 驟2 1 0與第五清洗步驟2 2 4的清洗、宜该在备— ' 月，无吟液係為氫氧化銨與過 氧化氫之水洛液（SCI)’第三清洗步 鄉220的清洗溶液係為 硫酸與過氧化氩溶液（SPM)，而篦-、主丄 示一h洗步驟2 1 2、第四清 洗步驟222與第六清洗步驟226 < β洗溶液係為超純水。 本發明的特點在於為除去相移或 %九罩上的殘留黏膠， 』^ —-----tr-------- (請先閱讀背面之注意事項再填寫本頁) 508642Mixture, APM, also known as SCI or HA), in addition to the second cleaning step 22 between the first cleaning step 120 and the third cleaning step 124, and the fourth cleaning step after the third cleaning step 1 24 The cleaning solution is ultra pure water (DI · Water; also known as deionized water), which can remove the residual cleaning solution. In this way, the cleaning process of the phase-shifting photomask can be completed. The conventional cleaning process sequentially uses four cleaning solutions of sulfuric acid and hydrogen peroxide solution (SPM), ultrapure water, aqueous solution of ammonium hydroxide and hydrogen peroxide (SCi), and ultrapure water. Among them, SPM is used to remove larger organic molecules, SCI is used to remove smaller organic molecules and fine particles, and ultrapure water is used to remove the first residual cleaning solution. However, · The viscose on the phase-shift mask used in general photomasks is an ester structure, (RCOOR) x, such as a polymer structure of polyacrylate. When the photomask is immersed in the cleaning tank of SPM, (RCOOR) x will hydrolyze to form a flowable but water-insoluble colloidal substance, (RCOOH) x. Therefore, during the cleaning process of the phase shift mask, (RCOOH) x may flow into the phase shift layer area and chemically react with the nitrogen atom (N) on the molybdenum silicon oxide (MoSiON) to form an Contaminants, (RCOO) NOSiMo, cause defects in the mask pattern and scrap of the mask. Purpose and summary of the invention: In view of the disadvantages of the conventional cleaning process described above, the standard paper size of the present invention is applicable to the Chinese national standard (CNSM4 specification (210 X 297 mm) l · ---- · --- 7- --Fee -------- Order -------: Line · (Please read the notes on the back before filling out this page) 5ι A7 V. Description of the invention (), provides a phase shift type The cleaning process of the photomask can completely remove the adhesive used in the photomask of the original device, and reduce the defects of the lithography process and the scrapping of the photomask. The cleaning process of the phase-shift photomask of the present invention includes: making the phase The mobile photomask is sequentially cleaned with the following cleaning solutions, water preparation solution of ammonium hydroxide and hydrogen peroxide (SC 1), ultrapure water, sulfuric acid and hydrogen peroxide solution, ultrapure water, and hydrogen peroxide. Aqueous solution of hydrogen peroxide; and ultrapure water. The cleaning process of the phase shift photomask of the present invention is used before the normal cleaning process of the phase shift photomask, that is, before the normal cleaning process of the phase shift photomask. Hydrogen peroxide and hydrogen peroxide aqueous solution (SCI) was used to clean the phase mask, and then ultrapure water was used to After washing, the cleaning process of general suitable photomask can be performed. In the above-mentioned aqueous solution of ammonium hydroxide and hydrogen peroxide (SCI), the volume ratio of water to ammonium oxide and hydrogen peroxide is 1 ·· X: Υ, After the father, the air decoration is less than or equal to 1 and the divination is less than or equal to 1, and the s C 1 solution is soaked for about 1 minute to the 58th dream, preferably for about 2 minutes. I -----; --- T --- -------- Order · (Please read the precautions on the back before filling out this page} Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Online Economics. Micro. It is not high in the commission system and wasted, and the cleaned-in order is reported. The dryness of the hood is cleaned. The dry phase is removed. The stain is removed. The bright light is dyed. The stain is reduced. The paper size is applicable to Chinese national standards. (CNS) A4 specification (21 × x 29 / Meal) 508642 A? B7 Meaning 5. Description of the invention (Simplified illustration of the drawings: The preferred embodiment of the present invention will be supplemented by the following figures in the following explanatory text. Explain in detail 'Among them · Figure 1 shows a phase-shifting photomask with a photomask generally shown in Figure 2 Shown is a schematic diagram of a phase-shifting reticle with the photomask removed in general. Figure 3 is a flowchart of a conventional phase-shifting reticle cleaning process; I — — — — — — — — — — — ' t I Please read the note on the back before filling this page) and Figure 4 shows the process flow diagram of the phase-shifting photomask cleaning process of the present invention. : 10 photomask 12 non-pattern area 14 pattern area 16 quartz transparent area 18 phase shift layer 20 photomask 120 first cleaning step 122 second cleaning step 124 third cleaning step 126 fourth cleaning step 210 first cleaning step 212 The second cleaning step 220 The third cleaning step 222 The fourth cleaning step 4 This paper size applies the Chinese National Standard (CNS) A4 specification (210x297 meal) 508642 V. Description of the invention (224) The fifth cleaning step 226 The sixth cleaning step is economical Printed by the Intellectual Property Bureau of the Ministry of Intellectual Property and Consumer Cooperatives, the detailed description of the invention: In view of the above-mentioned conventional cleaning process, the adhesive of the residual photoresist film in the phase-shift photomask cannot be removed, and The phase shift layer flows into the washing process and reacts with Mo Si ON. In this way, the residue of the adhesive is left in the pattern area of the photomask, and cannot be removed by any cleaning process, which not only causes wafer lithography Defects in the manufacturing process may even cause damage to the photomask. Therefore, the object of the present invention is to provide a cleaning process for a phase-shifting photomask, which can completely remove the adhesive used in the photoresist film of the original device without causing any residual phenomenon. Figure 4 shows the photomask cleaning process of the present invention = process diagram. Please refer to Section 4 ® 'Phase-shifted optical military system using the first cleaning step 21, the second cleaning step 212, and the third cleaning step 22 〇, a fourth cleaning step 222, a fifth cleaning step 224, a washing step, and a π washing step 226 are performed to complete the cleaning process of the phase-shifting photomask. Among them, the first cleaning step 2 10 and the fifth cleaning step 2 2 4 should be prepared — 'Month, the non-yin solution is ammonium hydroxide and hydrogen peroxide water solution (SCI)' third The cleaning solution of the cleaning step 220 is sulfuric acid and argon peroxide solution (SPM), and 篦-and 丄 are shown in an hour washing step 2 1 2. The fourth washing step 222 and the sixth washing step 226 < β washing solution Department of ultra-pure water. The feature of the present invention is that in order to remove the phase shift or residual adhesive on the hood, "^ -------- tr -------- (Please read the precautions on the back before filling this page) 508642
五、發明說明（） (RCOOR)x，係利用SC1的驗性特性，將（RC〇〇R)x水解為 可溶於水的銨鹽類，（RC00-NH4 + )x，如此可由洗滌之水溶 液將上述離子帶走。後續再利用SPM去除有機物的大分 子，SC 1來去除有機物之小分子與微粒子，並辅以超純水 沖洗殘留的洗淨液，如此可將相移式光罩上的黏膠與污垢 完全去除。本發明相移式光罩之清洗製程中，上述清洗槽 2 1 0的清洗溶液中，水、氫氧化銨與過氧化氫的體積比為 1 : X : Y，其中X係約小於等於1，Y係約小於等於i，視 產品需要可有所更改。另外，浸泡上述清洗槽2丨〇之清洗 溶液約1分鐘至5分鐘，較佳係浸泡約2分鐘，即可將相 移式光罩上的黏膠水解完全。 經濟部智慧財產局員工消費合作社印製 本發明相移式光罩之清洗製程，即在一般進行正常清 洗製程之前，加入一預清洗製程，利用一鹼性溶液清洗相 移式光罩’其目的在利用驗性溶液讓相移式光罩中的黏膠 結構’（RCOOR)x，形成可水解的鹽類。如此再進行下一步 的超純水洗滌，可將鹽類帶走，即可完全去除殘留在相移 式光罩上的黏膠。另外，由於一般相移式光罩的正常清洗 製程係為依序利用硫酸與過氧化氫溶液（SPM)、超純水、氫 氧化銨與過氧化氫之水溶液（S c 1 )、以及超純水來進行洗 條，其中SCI即為一鹼性水溶液，因此，即可利用SCI來 做為相移式光罩之預清洗製程中所需的鹼性溶液。 8 本紙張翻巾關賴準（CNS)A4麟（21G χ 297公餐） 508642 A7 B7 五、發明說明（ 本發明相移式光罩之清洗製程多加入sci與超純水的 洗蘇㈣，不僅使原I置光罩護媒所使用的黏料完全去 除，更可降低光罩上的微粒子污染，如此可進行效果較佳 的微影製程’並減低光罩報廢所耗損的成本。 如熟悉此技術之人員所瞭解的，以上所述僅為本發明 之較佳實施例而已，並非用以限定本發明之申請專利範 圍；凡其它未脫離本發明所揭示之精神下所完成之等效改 變或修飾，均應包含在下述之申請專利範圍内。 (請先閱讀背面之注意事項再填寫本頁) --------訂--------•線秦 經濟部智慧財產局員工消費合作社印製 9 本紙張尺度適用中國國家標準（CNS)A4規格（210 x 297公釐）V. Description of the invention () (RCOOR) x, which uses the experimental characteristics of SC1 to hydrolyze (RC〇〇R) x into water-soluble ammonium salts, (RC00-NH4 +) x, so that it can be washed by The aqueous solution removes the above ions. Later, SPM is used to remove large molecules of organic matter, and SC 1 is used to remove small molecules and fine particles of organic matter, and supplemented with ultrapure water to rinse the remaining cleaning solution, so that the adhesive and dirt on the phase-shifting photomask can be completely removed. . In the cleaning process of the phase-shifting photomask of the present invention, the volume ratio of water, ammonium hydroxide, and hydrogen peroxide in the cleaning solution of the cleaning tank 2 10 is 1: X: Y, where X is about 1 or less, Y is less than or equal to i, which can be changed according to the needs of the product. In addition, immersing the cleaning solution in the cleaning tank 2 〇 for about 1 minute to 5 minutes, preferably about 2 minutes, can completely hydrolyze the adhesive on the phase shift mask. The consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs printed the cleaning process of the phase-shifting photomask of the present invention, that is, before the normal cleaning process is generally performed, a pre-cleaning process is added, and the phase-shifting photomask is cleaned with an alkaline solution. The viscose structure '(RCOOR) x in the phase-shifting photomask is formed using a test solution to form hydrolyzable salts. This way, the next step of ultra-pure water washing can take away the salts and completely remove the adhesive left on the phase shift mask. In addition, since the normal cleaning process of a general phase-shifting photomask is to sequentially use sulfuric acid and hydrogen peroxide solution (SPM), ultrapure water, ammonium hydroxide and hydrogen peroxide aqueous solution (S c 1), and ultrapure The strip is washed with water, and SCI is an alkaline aqueous solution. Therefore, SCI can be used as the alkaline solution required in the pre-cleaning process of the phase-shifting photomask. 8 This paper turning towel depends on the standard (CNS) A4 Lin (21G χ 297 meals) 508642 A7 B7 V. Description of the invention (The cleaning process of the phase-shifting photomask of the present invention adds sci and ultrapure water for washing. Not only can the sticky material used for the original photomask protective medium be completely removed, but also the particle contamination on the photomask can be reduced, so that a better lithography process can be performed and the cost of photomask scrapping can be reduced. If familiar Those skilled in the art understand that the above description is only a preferred embodiment of the present invention and is not intended to limit the scope of patent application of the present invention; any other equivalent changes made without departing from the spirit disclosed by the present invention Or modification should be included in the scope of patent application below. (Please read the precautions on the back before filling this page) -------- Order -------- • Xinqin Ministry of Economy Wisdom Printed by the Property Bureau's Consumer Cooperatives 9 This paper size applies to China National Standard (CNS) A4 (210 x 297 mm)