TW200537258A - Method of stripping positive photoresist film, method of manufacturing mask for exposure, and apparatus for stripping photoresist - Google Patents
Method of stripping positive photoresist film, method of manufacturing mask for exposure, and apparatus for stripping photoresist Download PDFInfo
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- TW200537258A TW200537258A TW094109303A TW94109303A TW200537258A TW 200537258 A TW200537258 A TW 200537258A TW 094109303 A TW094109303 A TW 094109303A TW 94109303 A TW94109303 A TW 94109303A TW 200537258 A TW200537258 A TW 200537258A
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- A—HUMAN NECESSITIES
- A63—SPORTS; GAMES; AMUSEMENTS
- A63H—TOYS, e.g. TOPS, DOLLS, HOOPS OR BUILDING BLOCKS
- A63H33/00—Other toys
- A63H33/04—Building blocks, strips, or similar building parts
- A63H33/06—Building blocks, strips, or similar building parts to be assembled without the use of additional elements
- A63H33/08—Building blocks, strips, or similar building parts to be assembled without the use of additional elements provided with complementary holes, grooves, or protuberances, e.g. dovetails
- A63H33/084—Building blocks, strips, or similar building parts to be assembled without the use of additional elements provided with complementary holes, grooves, or protuberances, e.g. dovetails with grooves
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- A—HUMAN NECESSITIES
- A63—SPORTS; GAMES; AMUSEMENTS
- A63H—TOYS, e.g. TOPS, DOLLS, HOOPS OR BUILDING BLOCKS
- A63H33/00—Other toys
- A63H33/04—Building blocks, strips, or similar building parts
- A63H33/06—Building blocks, strips, or similar building parts to be assembled without the use of additional elements
- A63H33/08—Building blocks, strips, or similar building parts to be assembled without the use of additional elements provided with complementary holes, grooves, or protuberances, e.g. dovetails
- A63H33/082—Building blocks, strips, or similar building parts to be assembled without the use of additional elements provided with complementary holes, grooves, or protuberances, e.g. dovetails with dovetails
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- A—HUMAN NECESSITIES
- A63—SPORTS; GAMES; AMUSEMENTS
- A63H—TOYS, e.g. TOPS, DOLLS, HOOPS OR BUILDING BLOCKS
- A63H33/00—Other toys
- A63H33/04—Building blocks, strips, or similar building parts
- A63H33/06—Building blocks, strips, or similar building parts to be assembled without the use of additional elements
- A63H33/08—Building blocks, strips, or similar building parts to be assembled without the use of additional elements provided with complementary holes, grooves, or protuberances, e.g. dovetails
- A63H33/086—Building blocks, strips, or similar building parts to be assembled without the use of additional elements provided with complementary holes, grooves, or protuberances, e.g. dovetails with primary projections fitting by friction in complementary spaces between secondary projections, e.g. sidewalls
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- Photosensitive Polymer And Photoresist Processing (AREA)
- Preparing Plates And Mask In Photomechanical Process (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
Abstract
Description
200537258 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種在光罩、或半導體裝置、液晶顯示裝 置等之影像元件之製造步驟所使用之正型光阻膜之剝離方 法、及使用正型光阻膜之曝光用光罩之製造方法、以及光 阻剝離裝置。 【先前技術】 向來，藉由使用光罩之微影技術而進行半導體裝置或顯 Φ 示裝置之製造。該光罩係在玻璃等之基板上，形成由金屬 等之薄膜所構成之微細圖案（轉印圖案），使用來藉由搭載 光罩之曝光裝置（圖案轉印裝置）而進行微細圖案對於被 轉印體（附有光阻膜之元件基板）之圖案轉印。200537258 IX. Description of the invention: [Technical field to which the invention belongs] The present invention relates to a method for peeling a positive-type photoresist film used in a manufacturing step of a photomask, or a semiconductor device, an image element of a liquid crystal display device, and the like. Manufacturing method of exposure mask for positive type photoresist film, and photoresist peeling device. [Previous Technology] Conventionally, semiconductor devices or display devices have been manufactured by lithography using a photomask. The photomask is formed on a substrate such as glass, and forms a fine pattern (transfer pattern) made of a thin film such as metal, and is used to perform a fine pattern on the substrate by an exposure device (pattern transfer device) equipped with a photomask. Pattern transfer of transfer body (element substrate with photoresist film).
半導體裝置係一般使用縮小投影曝光裝置（步進器）所 製造，在該狀態下，光罩上之圖案係縮小投影成為例如1 / 5之大小。另一方面，在液晶顯示裝置（L i q u i d C r y s t a 1 Display:以下，稱為LCD)等之顯示裝置之製造，另外將 成為使用等倍率之總括曝光方式之曝光裝置之光罩對準器 予以使用。在步進器用之光罩和光罩對準器用之光罩，光 罩之尺寸係不同。步進器用之光罩（標線板）係一般為5 英 11 寸角（127mmxl27mm)或 6 英忖角（152.4mmxl52.4mm) 之正方形，但是，在光罩對準器用之光罩之狀態下，根據 監視器及TV顯示晝面尺寸而一般成為長方形，尺寸也大於 標線板（任何一邊皆成為3 0 0 m m以上），因此，稱為大型光 罩。接著，該大型光罩係由於顯示晝面之大面積化以及一 6 312XP/發明說明書(補件)/94-07/94109303 200537258 次製造許多畫面之要求等而有基板之尺寸更加大型化之傾 向發生。 但是，該光罩係使用在成為其原版之基板上形成上述薄 膜之光罩毛胚，藉由在其薄膜形成既定之微細圖案所得 到。光罩之一般製造步驟係在參考圖2而進行說明時，正 如以下。 首先，準備在石英玻璃等之透明基板上形成由金屬或其 合金等之材質所構成之遮光性薄膜之光罩毛胚（S 2 1 )。接 Φ 著，在該光罩毛胚上之整個面，形成光阻膜（S22)。通常 在光阻膜塗敷於光罩毛胚上之後，進行加熱處理（預烘 烤）。作為光阻係有藉由交聯反應等而硬化曝光之部位來不 溶化於顯影液之負型光阻以及曝光之部位成為低分子化而 溶解於顯影液之正型光阻之2種類，但是，隨著近年來之 光罩圖案之高微細化之要求而大多使用正型光阻。 接著，藉由在附有該光阻膜之光罩毛胚，進行既定之圖 案描繪（曝光）（S 2 3 )，使用顯影液，來進行顯影處理（S 2 4 )，The semiconductor device is generally manufactured using a reduced projection exposure device (stepper). In this state, the pattern on the photomask is reduced to a size of, for example, 1/5. On the other hand, in the manufacture of liquid crystal display devices (Liquid Crystal 1 Display: hereinafter referred to as LCD) and other display devices, a mask aligner is used as an exposure device that uses a uniform exposure method of collective magnification. . The size of the reticle is different between the reticle used for the stepper and the reticle used for the reticle aligner. The mask (marking plate) for stepper is generally a square of 5 inches 11 inches (127mmxl27mm) or 6 inches (152.4mmxl52.4mm), but in the state of the mask used for the mask aligner According to the size of the monitor and TV display daytime, it is generally rectangular, and the size is larger than the reticle (both sides are more than 300 mm), so it is called a large photomask. Next, the large photomask has a tendency to increase the size of the substrate due to the increase in the area of the daytime display and the requirements of 6 312XP / Invention Specification (Supplement) / 94-07 / 94109303 200537258 for the production of many screens occur. However, this photomask is obtained by using a photomask blank in which the above-mentioned film is formed on a substrate which is the original, and forming a predetermined fine pattern on the film. The general manufacturing steps of the photomask are described below with reference to Fig. 2 as follows. First, a mask blank (S 2 1) is formed on a transparent substrate such as quartz glass to form a light-shielding film made of a material such as metal or its alloy. Then, a photoresist film is formed on the entire surface of the mask blank (S22). After the photoresist film is applied to the photomask blank, it is usually heat-treated (pre-baked). As the photoresist, there are two types of negative photoresist that are not dissolved in the developing solution by hardening the exposed portion by a crosslinking reaction or the like, and two types of positive photoresist that are reduced in molecule and dissolved in the developing solution. In recent years, with the demand for a high degree of miniaturization of a mask pattern, a positive type photoresist is mostly used. Next, a predetermined pattern drawing (exposure) is performed on the photomask blank with the photoresist film attached thereto (S 2 3), and a developing solution is used to perform a development process (S 2 4).
而在光罩毛胚，形成光阻圖案。 接著，以該光阻圖案作為光罩，藉由蝕刻而除去露出之 遮光性薄膜（S 2 5 )。像這樣，完成在基板上使得遮光性薄 膜形成為既定之圖案狀之光罩。殘留之光阻圖案係使用專 用之光阻剝離液而進行剝離及除去（S 2 6 )。 仍然，除此之外，知道有：在基板上將反射曝光用光之 多層反射膜和吸收曝光用光之圖案狀吸收體膜予以形成之 反射型光罩、或者是在基板上形成相位移膜之相位移光 7 312XP/發明說明書(補件)/94-07/94109303 200537258 罩、或者是液晶顯示裝置之製造所使用之在基板上形成遮 光部、灰色調部及透光部之灰色調光罩等，但是，即使是 就這些光罩而言，也使用相同於前面敘述之同樣之微影步 驟而進行製造。 此外，即使是在使用光罩之半導體裝置或液晶顯示裝置 等之影像元件之製造，也使用微影步驟。In the photomask blank, a photoresist pattern is formed. Next, using this photoresist pattern as a photomask, the exposed light-shielding film is removed by etching (S 2 5). In this manner, a mask for forming a light-shielding thin film into a predetermined pattern on the substrate is completed. The remaining photoresist pattern is peeled and removed using a special photoresist stripping solution (S 2 6). Still, in addition to this, it is known to form a reflective mask including a multilayer reflective film that reflects light for exposure and a patterned absorber film that absorbs light for exposure, or a phase shift film on the substrate. Phase-shifted light 7 312XP / Invention Specification (Supplement) / 94-07 / 94109303 200537258 Cover, or gray dimming for forming a light-shielding part, a gray tone part, and a light transmission part on a substrate used in the manufacture of a cover or a liquid crystal display device Masks and the like are manufactured using the same lithographic steps as described above, even for these masks. In addition, the lithography process is used even in the manufacture of imaging devices such as semiconductor devices using liquid masks or liquid crystal display devices.
但是，在微影步驟結束後，成為不必要之光阻圖案係一 般正如前面敘述，使用專用之光阻剝離液（光阻廠商所販 賣）而進行剝離及除去。此外，在專利文獻1，揭示：藉 由使得臭氧氣體和光阻膜除去溶液（或者是含臭氧氣體之 光阻膜除去溶液）接觸到光阻膜而對於光阻膜進行氧化分 解及除去之光阻膜之除去方法。 但是，在使用上述專用光阻剝離液之方法之狀態下，在 光阻剝離之本身，特別並無問題發生，但是，使用光阻剝 離液之成分在消防法或各種環境法成為管理對象之藥品， 因此，當然除了未使用之光阻剝離液之管理以外，即使是 在廢液，也需要嚴密之管理，廢液處理費用係壓迫到成本。 特別是在大型光罩之狀態下，基板尺寸變大，因此，光阻 剝離液之使用量係需要大量，由於近年來之基板尺寸之大 型化之傾向而使得問題成為更加深刻化之方向。 此外，在上述專利文獻1所揭示之光阻膜之除去方法之 狀態下，如果使用例如純水、酸性水溶液或鹼性水溶液等 來作為光阻膜除去溶液的話，則不需要根據消防法或各種 環境法之所造成之特別管理，即使是在環境面，也進行改 8 3】2XP/發明說明書(補件)/94-07/94109303 200537258 善，但是，具備臭氧氣體供應管或者是對於臭氧氣體及/ 或光阻膜除去溶液來進行回收處理之處理槽等，此外，需 要用以使得導入之臭氧氣體或者是在光阻膜除去步驟之所 產生之氣體、蒸氣等以仍然之狀態而不釋出之密閉容器所 構成之昂責且專用之光阻膜除去裝置，因此，其費用係成 為壓迫成本之要因。However, after the lithography step, unnecessary photoresist patterns are generally used as described above, and a special photoresist stripping solution (sold by a photoresist manufacturer) is used for stripping and removal. In addition, Patent Document 1 discloses a photoresist that undergoes oxidative decomposition and removal of a photoresist film by bringing an ozone gas and a photoresist film removal solution (or a photoresist film removal solution containing ozone gas) into contact with the photoresist film. How to remove the film. However, in the state where the above-mentioned special photoresist stripping solution is used, there is no problem in particular in the photoresist stripping itself. However, the components using the photoresist stripping solution are controlled by the fire protection method or various environmental laws. Therefore, of course, in addition to the management of the unused photoresist stripping solution, even in the waste liquid, strict management is needed, and the waste liquid treatment cost is pressing to cost. Especially in the state of a large photomask, the size of the substrate becomes large. Therefore, a large amount of photoresist stripping solution is used. The problem has become a deeper direction due to the tendency of the substrate size to be increased in recent years. In addition, in the state of the method for removing a photoresist film disclosed in the above-mentioned Patent Document 1, if pure water, an acidic aqueous solution, or an alkaline aqueous solution is used as the photoresist film removal solution, there is no need to comply with the fire protection method or various The special management caused by the environmental law will be changed even on the environmental level. 8] 2XP / Invention Manual (Supplement) / 94-07 / 94109303 200537258 Good, but it has an ozone gas supply pipe or is And / or a processing tank for recovering the photoresist film removal solution, etc. In addition, it is necessary to keep the introduced ozone gas or the gas, vapor, etc. generated in the photoresist film removal step in a still state. The responsible and dedicated photoresist film removal device constituted by the closed container, so its cost has become a major factor in suppressing the cost.
作為對於上述問題之方法係例如在專利文獻2，揭示： 在藉由利用照射紫外線來曝光及顯影殘留之光阻圖案而剝 離光阻圖案之方法，為了完全地除去光阻殘渣，因此，旋 轉基板，同時，由紫外線照射燈，來照射紫外線，藉由設 置在曝光室内壁之反射鏡，而將照射光，照射於光阻膜之 整個面之方法。 (專利文獻1 )日本專利特開2 0 0 0 — 1 4 7 7 9 3號公報 (專利文獻2 )日本專利特開平6 — 1 6 4 1 0 1號公報 【發明内容】 (發明所欲解決之問題） 但是，專利文獻2所記載之方法係需要具有旋轉機構之 裝置，例如在處理液晶面板或其製造所使用之大型光罩之 大型基板之狀態下，需要大型且大規模之處理裝置，因此， 變得不適合。 因此，本發明之目的係解決習知之問題點，提供一種不 需要根據消防法或各種環境法之所造成之特別管理並且能 夠以低成本來進行處理而且即使是對於大型基板也不需要 大型且大規模之處理裝置的正型光阻膜之剝離方法及曝光 9 312XP/發明說明書(補件)/94-07/94109303As a method for solving the above-mentioned problems, for example, Patent Document 2 discloses a method of peeling a photoresist pattern by exposing and developing a remaining photoresist pattern by irradiating ultraviolet rays. In order to completely remove photoresist residues, a substrate is rotated. At the same time, a method of irradiating ultraviolet rays with an ultraviolet irradiation lamp and irradiating the entire surface of the photoresist film with a irradiated light through a reflecting mirror provided on the inner wall of the exposure chamber. (Patent Document 1) Japanese Patent Laid-Open No. 2 0 0 — 1 4 7 7 9 3 (Patent Document 2) Japanese Patent Laid-Open No. 6 — 1 6 4 1 0 [Content of the Invention] (Inventive Solution (Problem) However, the method described in Patent Document 2 requires a device having a rotating mechanism. For example, a large-scale and large-scale processing device is required in the state of processing a large-size substrate of a liquid crystal panel or a large photomask used in its manufacture. Therefore, it becomes unsuitable. Therefore, an object of the present invention is to solve a conventional problem, to provide a method that does not require special management in accordance with fire protection laws or various environmental laws, and can be processed at low cost, and does not require large and large substrates even for large substrates. Method and exposure of positive photoresist film for large-scale processing equipment 9 312XP / Invention Manual (Supplement) / 94-07 / 94109303
200537258 用光罩之製造方法、以及光阻剝離裝置。 (解決問題之手段） 為了解決上述問題，因此，本發明係具有以下之構道 (構造1 ) 一種正型光阻膜之剝離方法，其特徵為： 藉由使得具有正型光阻膜之基板之光阻膜面和光照射手 相對地移動於既定之方向而曝光該光阻膜面後，藉由使 曝光之光阻膜，接觸到溶解經曝光之光阻之處理液，而 上述基板剝離及除去正型光阻膜。 (構造2 )如構造1所記載之正型光阻膜之剝離方法 其特徵為：具有上述正型光阻膜之基板係在設置於基板 之薄膜，具有在藉由施行包含正型光阻膜之曝光步驟及 影步驟之圖案化步驟而形成既定圖案後之殘留之正型光 膜的基板。 (構造3 )如構造2所記載之正型光阻膜之剝離方法 其特徵為：上述處理液係使用在上述顯影步驟所使用之 φ 影液。 (構造4 ) 一種曝光用光罩之製造方法，係藉由在基 上設置成為轉印光罩圖案之薄膜之光罩毛胚上形成既定 正型光阻圖案，並且以該光阻圖案作為光罩，蝕刻露出 上述薄膜而進行圖案化步驟者，其特徵為：在上述圖案 步驟後，藉由使得殘留之光阻圖案和光照射手段相對地 動於既定之方向而曝光該光阻圖案後，藉由接觸到溶解 曝光之光阻之處理液，而剝離及除去光阻圖案。 (構造5 )如構造4所記載之曝光用光罩之製造方法 312XP/發明說明書(補件)/94-07/94109303 在 段 得 由 ， 上 顯 阻 j 顯 板 之 之 化 移 經 10 200537258 其特徵為：作為上述處理液係使用在上述光罩毛胚上形成 既定之光阻圖案時所使用之顯影液，且利用在上述光罩毛 胚上形成既定之光阻圖案時之顯影手段，接觸到上述顯影 液。 (構造6 ) —種光阻剝離裝置，係用以藉由在對於具有 正型光阻膜之基板之光阻膜面進行曝光後，使得曝光之光 阻膜，接觸到溶解經曝光之光阻之處理液，而由上述基板 剝離及除去正型光阻膜者，其特徵為具有：曝光室，其具200537258 Manufacturing method of photomask and photoresist peeling device. (Means for Solving the Problem) In order to solve the above problems, the present invention has the following constitution (Structure 1) A method for stripping a positive type photoresist film, which is characterized in that: by making a substrate having a positive type photoresist film After the photoresist film surface and the light irradiating hand are relatively moved in a predetermined direction to expose the photoresist film surface, the exposed photoresist film is brought into contact with a processing solution that dissolves the exposed photoresist, and the substrate is peeled and removed. Remove the positive photoresist film. (Structure 2) The method for peeling a positive-type photoresist film as described in Structure 1 is characterized in that the substrate having the above-mentioned positive-type photoresist film is a thin film provided on the substrate, and has a positive-type photoresist film included in the substrate. The patterning step of the exposure step and the shadowing step forms a substrate of a positive light film remaining after a predetermined pattern. (Structure 3) The method for peeling a positive-type photoresist film as described in Structure 2 is characterized in that: the processing liquid is a φ shadow liquid used in the development step. (Structure 4) A method for manufacturing a photomask for exposure is to form a predetermined positive photoresist pattern on a photomask blank of a film that is a transfer photomask pattern on the substrate, and use the photoresist pattern as light. A person who performs a patterning step by etching and exposing the thin film, is characterized in that after the patterning step, the photoresist pattern is exposed by moving the remaining photoresist pattern and light irradiation means in a predetermined direction, and then It comes into contact with a treatment solution that dissolves the exposed photoresist, and peels and removes the photoresist pattern. (Structure 5) The manufacturing method of the exposure mask described in Structure 4 312XP / Invention Manual (Supplement) / 94-07 / 94109303 In the paragraph above, the resistance of the display board is obviously shifted by 10 200537258 which It is characterized in that: as the treatment liquid, a developing solution used when forming a predetermined photoresist pattern on the photomask blank is used, and a developing means is used to form a predetermined photoresist pattern on the photomask blank. To the developer. (Structure 6) —A photoresist stripping device is used to expose the exposed photoresist film to the exposed photoresist by exposing the photoresist film surface of a substrate having a positive photoresist film. The processing liquid, and the positive type photoresist film is peeled off and removed from the substrate, which is characterized by: an exposure chamber, which has
有保持上述基板之保持手段、和對向於上述基板之光阻膜 面所設置之光照射手段；處理室，其具有保持上述基板之 保持手段、和在上述基板之光阻膜面供應溶解經曝光之光 阻之處理液的處理液供應手段，且剝離及除去曝光之光 阻；以及基板搬送手段，其將上述基板由上述曝光室搬送 至上述處理室。 (構造7 )如構造6所記載之光阻剝離裝置，其特徵為： φ 保持上述曝光室和上述處理室之基板之保持手段係保持上 述基板之光阻膜面朝向斜上方傾斜。 如果藉由構造1的話，則本發明之正型光阻膜之剝離方 法係在對於具有正型光阻膜之基板之光阻膜面來進行曝光 後，藉由使得曝光之光阻膜，接觸到溶解曝光之光阻之處 理液，而由基板，來剝離及除去正型光阻膜。 正型光阻係在進行曝光時，藉由其照射能而切斷高分子 之主鏈，進行低分子化，因此，對於既定之處理液，成為 可溶性。所以，如果藉由構造1之方法的話，則可以藉由 11 3 ] 2XP/發明說明書(補件)/94-07/94109303There are holding means for holding the substrate, and light irradiation means provided to the photoresist film surface of the substrate; a processing chamber having holding means for holding the substrate, and supplying a dissolving process on the photoresist film surface of the substrate A processing liquid supply means for the processing solution for the exposed photoresist, and the photoresist for the exposure is peeled off and removed; and a substrate transfer means for transferring the substrate from the exposure chamber to the processing chamber. (Structure 7) The photoresist peeling device according to Structure 6, characterized in that: [phi] The holding means for holding the substrates of the exposure chamber and the processing chamber is to hold the photoresist film surface of the substrate to incline obliquely upward. If the structure 1 is adopted, the method for stripping the positive-type photoresist film of the present invention is after exposing the photoresist film surface of a substrate having a positive-type photoresist film, and then exposing the exposed photoresist film to contact The positive photoresist film is peeled off and removed from the substrate by dissolving the exposed photoresist processing solution. The positive type photoresist is used to cut the main chain of the polymer by its irradiation energy to reduce the molecular weight during exposure. Therefore, it becomes soluble in a predetermined treatment solution. Therefore, if the method of structure 1 is adopted, then 11 3] 2XP / Invention Specification (Supplement) / 94-07 / 94109303
200537258 對於光阻膜來進行曝光之步驟以及接著使得光阻膜接觸 既定之處理液之步驟，而由基板，來剝離及除去正型光 膜，能夠利用簡便之步驟而以低成本，來進行處理。此夕丨 上述溶解曝光之光阻之處理液係可以不需要根據消防法 各種環境法之所造成之特別管理，因此，能夠減低廢液 理等之成本。此外，如果藉由構造1的話，則藉由使得 阻膜面和光照射手段呈相對地移動於既定之方向而曝光 光阻膜面，因此，即使是不使用旋轉機構，也可以對於 型基板，在光阻面之整個面照射光。 例如正如構造2，可以在設置於基板上之薄膜，在藉 施行包含正型光阻膜之曝光步驟及顯影步驟之圖案化步 而形成既定圖案後，使用上述構造1之方法而剝離及除 殘留之正型光阻膜。該狀態下之正型光阻膜係形成於基 上之薄膜上之圖案狀光阻膜，以該光阻圖案作為光罩， 由蝕刻而除去露出之薄膜，在基板上之薄膜，形成既定 圖案。像這樣，在基板上之薄膜形成既定之圖案後，不 要殘留之光阻圖案，必須除去。可以藉由構造1之方法 曝光殘留之光阻圖案，接著，藉由使得光阻圖案接觸到 定之處理液，而由基板，僅剝離及除去光阻圖案。 此外，如果藉由構造3的話，則可以藉由使用在上述 影步驟所使用之顯影液，來作為上述處理液，而剝離及 去殘留之正型光阻膜。 因此，如果藉由構造3之方法的話，則來自殘留之光 圖案之基板之剝離除去係能夠對應在基板上之薄膜上形 312XP/發明說明書(補件)/94-07/94109303 到 阻 或 處 光 該 大 由 驟 去 板 藉 之 需 而 既 顯 除 阻 成 12200537258 For the step of exposing the photoresist film and the step of bringing the photoresist film into contact with a predetermined processing liquid, the substrate can be used to peel and remove the positive photo film, which can be processed at a low cost with simple steps. . At this time, the above-mentioned treatment solution for dissolving the exposed photoresist may not require special management caused by various fire protection laws and environmental laws, and therefore, the cost of waste liquid treatment and the like can be reduced. In addition, if the structure 1 is used, the photoresist film surface is exposed by moving the resist film surface and the light irradiation means relatively in a predetermined direction. Therefore, even without using a rotating mechanism, the substrate can be used in The entire surface of the photoresist surface is illuminated with light. For example, as in the structure 2, the thin film provided on the substrate can be peeled off and removed by using the method of the structure 1 after forming a predetermined pattern by performing a patterning step including an exposure step and a development step of a positive photoresist film. Positive photoresist film. The positive type photoresist film in this state is a patterned photoresist film formed on a film on the substrate. The photoresist pattern is used as a photomask to remove the exposed film by etching, and the film on the substrate is formed into a predetermined pattern. . In this manner, after a predetermined pattern is formed on a thin film on a substrate, a photoresist pattern that does not remain is required and must be removed. The remaining photoresist pattern can be exposed by the method of Structure 1, and then the photoresist pattern can be peeled and removed only from the substrate by bringing the photoresist pattern into contact with a predetermined processing liquid. In addition, if the structure 3 is used, the developing solution used in the above-mentioned shadowing step can be used as the processing solution, and the positive-type photoresist film can be peeled off and removed. Therefore, if the method of structure 3 is adopted, the peeling and removal of the substrate from the residual light pattern can correspond to the shape of the film on the substrate 312XP / Invention Specification (Supplement) / 94-07 / 94109303 to the resistance or place The light should be removed from the board by the sudden need to remove the resistance into 12
200537258 既定之光阻圖案時之顯影步驟。此外，一般使用之正型 阻之顯影液係不需要根據消防法或各種環境法之所造成 特別管理，因此，能夠減低廢液處理等之成本。此外， 剝離及除去光阻圖案時，使用正型光阻之顯影液，所以 不必恐怕基板上之薄膜發生變質。 此外，正如構造4所示，可以藉由在基板上設置成為 印光罩圖案之薄膜之光罩毛胚上來形成既定之正型光阻 案並且以該光阻圖案作為光罩來蝕刻露出之上述薄膜而 行圖案化步驟的曝光用光罩之製造方法，在上述圖案化 驟後而曝光殘留之光阻圖案後，藉由接觸到溶解曝光之 阻之處理液，而剝離及除去光阻圖案。也就是說，可以 由曝光光阻圖案之步驟和接著接觸到上述處理液之步驟 實施光阻之剝離，並且，可以不使用光阻剝離用之特別 品而實施，能夠利用簡便之步驟而以低成本來進行處理 此外，如果藉由構造4的話，則藉由使得光阻膜面和光 射手段呈相對地移動於既定之方向而曝光該光阻膜面， 此，即使是不使用旋轉機構，即使是對於大型光罩，也 夠在光阻面之整個面，來照射光。 此外，正如構造5所示，可以藉由使用在上述光罩毛 上形成既定之光阻圖案時之所使用之顯影液來作為上述 理液，使用在上述光罩毛胚上來形成既定之光阻圖案時 顯影手段，接觸到上述顯影液，而利用顯影裝置，來應 光阻之剝離，並且，一般使用之正型光阻之顯影液係不 要根據消防法或各種環境法之所造成之特別管理，因此 312XP/發明說明書(補件)/94-07/94109303 光 之 在 ， 轉 圖 進 步 光 藉 而 藥 〇 照 因 能 胚 處 之 對 需 13200537258 The development step for a predetermined photoresist pattern. In addition, the commonly used positive-develop developer does not require special management in accordance with the fire protection law or various environmental laws, so it can reduce the cost of waste liquid treatment and the like. In addition, when peeling and removing the photoresist pattern, a positive photoresist developing solution is used, so there is no need to fear that the film on the substrate will be deteriorated. In addition, as shown in Structure 4, the predetermined positive photoresist pattern can be formed by setting a photomask blank on the substrate as a film for printing a photomask pattern, and using the photoresist pattern as a photomask to etch and expose the above. The manufacturing method of a photomask for exposure in which a thin film is patterned in a patterning step, after the patterning step is performed, the remaining photoresist pattern is exposed, and the photoresist pattern is peeled off and removed by contacting a treatment solution that dissolves the exposed resist. That is, the photoresist can be peeled off from the step of exposing the photoresist pattern and then the step of contacting the processing solution, and can be carried out without using a special product for photoresist stripping. If the structure 4 is used, the photoresist film surface is exposed by moving the photoresist film surface and the light radiating means in a predetermined direction. Therefore, even if a rotating mechanism is not used, It is enough for large photomasks to illuminate the entire surface of the photoresist surface. In addition, as shown in Structure 5, it is possible to use the developer used when forming a predetermined photoresist pattern on the mask hair as the physical fluid, and use the developer on the photomask embryo to form a predetermined photoresist. When developing the pattern, the developing means comes into contact with the above-mentioned developer, and the developing device is used to respond to the peeling of the photoresist. In addition, the developer of the positive photoresist used in general is not subject to special management caused by the fire protection law or various environmental laws. Therefore, 312XP / Invention Specification (Supplement) / 94-07 / 94109303 The light is present, the picture is transferred to advance the light and the medicine is borrowed.
200537258 能夠減低廢液處理等之成本。此外，在剝離及除去光阻 案時，使用正型光阻之顯影液，所以，不必恐怕形成於 板上之轉印光罩圖案發生變質。 此外，如果藉由構造6之光阻剝離裝置的話，則可以 由利用對於光阻膜進行光照射之曝光室和供應既定之處 液至光阻膜之處理室，來進行光阻膜之處理，而由基板 來剝離及除去正型光阻膜，能夠利用簡便之步驟而以低 本來進行處理。此外，上述溶解曝光之光阻之處理液係 以不需要根據消防法或各種環境法之所造成之特別管理 因此，能夠減低廢液處理等之成本。此外，可以藉由使 基板搬送手段，而連續地進行藉由對於光阻膜之光照射 處理液之所造成之處理。 此外，如果藉由構造7的話，則保持曝光室和處理室 基板之保持手段係進行傾斜及保持而使得上述基板之光 膜面朝向斜上方，因此，比起基板之光阻膜面朝向正上 (水平）之狀態，還更加可以達到省空間化，所以，特 是適合於大型基板之處理。 (發明效果） 如果藉由本發明的話，則由基板來剝離及除去殘留於 板上並且成為不必要之狀態等之正型光阻膜，因此，實 對於光阻膜進行曝光之步驟和接著使得曝光之光阻膜接 到溶解曝光之光阻之處理液之步驟。可以藉此而由基板 剝離及除去正型光阻膜，能夠利用簡便之步驟而以低成 來進行處理。此外，在本發明，可以使用在顯影步驟所 312XP/發明說明書(補件)/94-07/94109303 圖 基 藉 理 成 可 用 和 之 阻 方 別 基 施 觸 來 本 使 14 200537258 用之顯影液，來作為進行正型光阻膜之剝離除去之處理 液，因此，可以不使用光阻膜剝離用之特別藥品而實施。 並且，一般使用之正型光阻之顯影液係不需要根據消防法 或各種環境法之所造成之特別管理，因此，廢液處理等係 可以進行於通常水準，所以，能夠減低廢液處理等之成本。 此外，如果藉由本發明的話，則藉由使得光阻膜面和光照 射手段呈相對地移動於既定之方向而曝光該光阻膜面，因 此，即使是不使用旋轉機構，也能夠對於大型基板，在光 阻面之整個面，來照射光。 此外，可以藉由適用由於本發明所造成之正型光阻膜之 剝離方法而達到曝光用光罩之製造成本之減低。 【實施方式】 以下，藉由實施形態而詳細地說明本發明。 作為本發明之實施形態係可以列舉例如以下之形態。 (實施形態1 )200537258 can reduce the cost of waste liquid treatment, etc. In addition, in the case of peeling and removing the photoresist, a positive photoresist developer is used, so there is no need to fear that the transfer mask pattern formed on the board is deteriorated. In addition, if the photoresist peeling device of structure 6 is used, the photoresist film can be processed by using an exposure chamber for light irradiation of the photoresist film and a processing chamber that supplies a predetermined liquid to the photoresist film. On the other hand, the positive-type photoresist film can be peeled off and removed from the substrate, and can be processed at a low cost with simple steps. In addition, the above-mentioned treatment solution for dissolving the exposed photoresist does not require special management in accordance with the fire protection law or various environmental laws. Therefore, the cost of waste liquid treatment and the like can be reduced. In addition, it is possible to continuously perform processing by irradiating the processing solution with light on the photoresist film by using a substrate transfer means. In addition, if the structure 7 is used, the holding means for holding the substrates of the exposure chamber and the processing chamber is tilted and held so that the light film surface of the substrate faces obliquely upward. Therefore, the photoresist film surface of the substrate faces upward. The (horizontal) state can also achieve space saving, so it is especially suitable for processing large substrates. (Effects of the Invention) According to the present invention, the substrate is used to peel off and remove the positive-type photoresist film remaining on the board and becoming unnecessary, etc. Therefore, the step of exposing the photoresist film and the subsequent exposure The photoresist film is connected to a solution for dissolving the exposed photoresist. This allows the positive-type photoresist film to be peeled off and removed from the substrate, and can be processed at a low cost with simple steps. In addition, in the present invention, the developer solution 312XP / Invention Manual (Supplement) / 94-07 / 94109303 can be used as a developer solution, which can be used in conjunction with the resistive method, and the developer solution used in 2005 14258, Since it is used as a treatment liquid for peeling and removing the positive-type photoresist film, it can be carried out without using a special medicine for peeling the photoresist film. In addition, the normally used positive photoresist developer does not require special management in accordance with the fire protection law or various environmental laws. Therefore, waste liquid treatment can be performed at normal levels, so waste liquid treatment can be reduced. Cost. In addition, according to the present invention, the photoresist film surface is exposed by moving the photoresist film surface and the light irradiation means relatively in a predetermined direction. Therefore, even without using a rotating mechanism, a large substrate can be used. Light is irradiated on the entire surface of the photoresist surface. In addition, it is possible to reduce the manufacturing cost of the photomask for exposure by applying the method for stripping the positive-type photoresist film caused by the present invention. [Embodiment] Hereinafter, the present invention will be described in detail through embodiments. Examples of embodiments of the present invention include the following. (Embodiment 1)
本發明之實施形態1係在對於具有正型光阻膜之基板之 光阻膜面來進行曝光後，藉由使得曝光之光阻膜接觸到顯 影液而由上述基板來剝離及除去正型光阻膜之正型光阻膜 之剝離方法。在本實施形態，作為溶解曝光之光阻膜之處 理液係使用正型光阻膜之顯影所使用之顯影液。 在上述實施形態1，作為基板上之所具有之上述正型光 阻膜係可以列舉例如在設置於基板上之薄膜藉由施行包含 藉著正型光阻膜之曝光步驟及顯影步驟來形成既定之光阻 圖案之步驟之圖案化步驟而形成既定之轉印光罩圖案後之 15 312XP/發明說明書(補件)/94-07/94109303 200537258 所殘留之正型光阻膜或者是失敗於光阻塗敷之正型光阻 膜。作為在基板上設置由單一或複數層所構成之薄膜而在 該薄膜形成既定之轉印光罩圖案之形態係列舉半導體裝置 或液晶顯示裝置等之製造所使用之曝光用光罩或半導體裝 置、液晶顯示裝置（液晶顯示面板）等。如果藉由上述實 施形態1的話，則可以在這些曝光用光罩或各種裝置之製 造步驟，在失敗於光阻塗敷而必須重新進行光阻塗敷之狀 態下，剝離及除去不良之正型光阻膜，並且，可以在圖案According to the first embodiment of the present invention, after the photoresist film surface of a substrate having a positive photoresist film is exposed, the exposed photoresist film is brought into contact with a developing solution to strip and remove the positive light from the substrate. Stripping method of positive photoresist film. In this embodiment, the physical liquid is a developer used for development using a positive type photoresist film as a place where the exposed photoresist film is dissolved. In the above-mentioned Embodiment 1, as the above-mentioned positive-type photoresist film on the substrate, for example, a thin film provided on the substrate may be formed by performing an exposure step and a development step including a positive-type photoresist film to form a predetermined film. 15 312XP / Invention Manual (Supplement) / 94-07 / 94109303 200537258 Residual positive photoresist film may fail in light after patterning the photoresist pattern Resistive coated positive type photoresist film. A series of single-layer or multiple-layer films are provided on a substrate to form a predetermined transfer mask pattern on the substrate. For example, exposure masks or semiconductor devices used in the manufacture of semiconductor devices or liquid crystal display devices. Liquid crystal display device (liquid crystal display panel), etc. According to the first embodiment, in the manufacturing steps of these exposure masks or various devices, it is possible to peel off and remove the defective positive type in a state where the photoresist coating fails and the photoresist coating must be re-applied. Photoresist film, and can be in the pattern
化之光步驟結束後，剝離及除去殘留之不必要之正型光阻 膜0 光阻膜係可以使用例如旋轉塗敷器、縫隙塗敷器或者是 藉由對於朝向於下方之塗敷面來使用毛細管現象而接收由 喷嘴開始上升之塗敷液並且呈相對地移動基板和喷嘴以便 於塗敷光阻之所謂C A P塗敷器等，來進行塗敷。 作為上述正型光阻係知道例如由聚丁烯一 1 一砜或聚環 φ 氧丙基甲基丙烯酸酯之比較高黏度之高分子樹脂所構成之 主鏈切斷型光阻、或者是由酚醛樹脂和溶解阻礙劑等之所 構成之溶解阻礙型光阻等。 藉由對於失敗於光阻塗敷之不良之正型光阻膜或者是 藉由施行圖案化步驟來殘留於基板上之正型光阻膜，進行 曝光處理，來得到對於顯影液之溶解性，接著，供應顯影 液，而剝離及除去成為不必要之光阻膜。 在該狀態下，曝光波長係可以是屬於正型光阻之感光波 長區域之波長。特別是可以照射對於上述正型光阻之高感 16 312XP/發明說明書(補件)/94-07/94109303After the photochemical step is completed, the unnecessary positive photoresist film is peeled off and removed. The photoresist film system can be used, for example, by a spin coater, a gap coater, or by The coating is performed using a so-called CAP applicator, etc., which receives a coating liquid rising from a nozzle by a capillary phenomenon, and moves the substrate and the nozzle relatively so as to apply a photoresist. As the above-mentioned positive type photoresist, for example, a main chain cut-off type photoresist composed of a polymer resin having a relatively high viscosity such as polybutene-1, sulfone, or polycyclic φ oxypropyl methacrylate, or A dissolution-blocking photoresist composed of a phenol resin and a dissolution inhibitor. The solubility of the developing solution is obtained by performing an exposure process on a positive photoresist film that fails due to photoresist coating or a positive photoresist film remaining on a substrate by performing a patterning step. Then, the developer is supplied, and peeling and removal become unnecessary photoresist films. In this state, the exposure wavelength may be a wavelength belonging to the photosensitive wavelength region of the positive type photoresist. In particular, it can illuminate the high sensitivity of the positive photoresistor 16 312XP / Invention Manual (Supplement) / 94-07 / 94109303
200537258 度之波長區域之曝光用光。此外，曝光量係以光阻之 除去，作為目的，因此，例如為了形成光阻圖案，所 最好是比起通常需要之曝光量，還賦予更多之曝光量 別是蝕刻光罩所使用之光阻圖案係有藉由蝕刻而在光 案之表面來形成表面改質層之狀態發生，因此，為了 該表面改質層，所以，最好是為了形成光阻圖案而賦 起通常需要之曝光量還更多之曝光量。 曝光方法係使用藉由使得具有正型光阻膜之基板之 阻膜面和光照射手段呈相對地移動於既定之方向而曝 光阻膜面之方法。具體地說，藉由使用延伸於基板之 方向之光照射手段，移動基板或光照射手段，而使得 射手段掃描於基板上，曝光基板上之光阻膜之整個面 以藉由使用該方法而對於大型基板，來容易地進行光 射，此外，可以對於複數個基板，來連續地進行光照 正如本實施形態，在使用由基板之上方開始進行光 光阻膜之照射之方法之光阻剝離，例如正如使用上述 塗敷器而進行塗敷之光阻膜，特別是適合於藉由在基 側面或背面不旋轉入光阻之塗敷方法而進行塗敷之光 之剝離。 在曝光處理後之所使用之顯影液係可以是配合於正 光阻材料之顯影液。除了使用之正型光阻材料之專用 液以外，並且，也以光阻之剝離除去，來作為目的，因 也可以不一定是專用顯影液，重要的是可以成為能夠 曝光之正型光阻材料之處理液。例如適合使用以氫氧 3】2XP/發明說明書(補件)/94-07/94 ] 09303 剝離 以， 。特 阻圖 除去 予比 光 光該 某一 光照 〇 可 昭 射。 對於 CAP 板之 阻膜 型 顯影 此， 溶解 化納 17200537258 Degree of exposure light in the wavelength region. In addition, the exposure amount is for the purpose of removing the photoresist. Therefore, for example, in order to form a photoresist pattern, it is better to give more exposure amount than the exposure amount that is usually required, especially for the etching mask. The photoresist pattern occurs in a state where a surface modification layer is formed on the surface of the photoresist by etching. Therefore, for this surface modification layer, it is best to give the photoresist pattern the exposure that is usually required More exposure. The exposure method is a method of exposing the resist film surface by relatively moving the resist film surface and the light irradiation means of a substrate having a positive-type resist film in a predetermined direction. Specifically, by using the light irradiation means extending in the direction of the substrate, the substrate or the light irradiation means is moved so that the irradiation means is scanned on the substrate, and the entire surface of the photoresist film on the substrate is exposed to use the method. For large substrates, light can be easily radiated. In addition, multiple substrates can be continuously irradiated. As in this embodiment, the photoresist peeling method using a method of irradiating a photoresist film from above the substrate is used. For example, a photoresist film coated by using the above-mentioned applicator is particularly suitable for peeling off the coated light by a coating method in which the photoresist is not rotated into the base side or the back surface. The developing solution used after the exposure process may be a developing solution mixed with a positive photoresist material. In addition to the special liquid used for the positive type photoresist material, it is also used for the purpose of stripping and removing the photoresist, because it may not necessarily be a special developer solution. It is important to be a positive type photoresist material that can be exposed. Of the processing fluid. For example, it is suitable to use hydrogen and oxygen 3] 2XP / Invention Specification (Supplement) / 94-07 / 94] 09303. The special resistance map removes a certain light, which can be radiated. For the resist type development of CAP plates, this dissolves sodium 17
200537258 (N a 0 Η )、氫氧化鉀（K 0 Η )等之鹼性物質作為主成分之 影液。這些顯影液係皆並無使用在消防法或各種環境法 為管理對象之藥品，因此，並不需要特別之管理，使得 理變得容易。 此外，在接觸到該狀態下之顯影液之方法，並無特別 限制，例如可以任意地選用：將具有光阻膜之基板來浸 於顯影液中之方法、或者是由具有光阻膜之基板上開始 淋浴狀地供應顯影液之方法、或者是藉由噴丨麗而吹附顯 液之方法等。 (實施形態2 ) 本發明之實施形態2係藉由在基板上設置成為轉印光 圖案之薄膜之光罩毛胚上，形成既定之正型光阻圖案， 該光阻圖案作為光罩來蝕刻露出之上述薄膜，而進行圖 化步驟，在曝光殘留之光阻圖案後，藉由接觸到顯影液 而剝離及除去光阻圖案的曝光用光罩之製造方法。 本實施形態係在曝光用光罩之製造步驟，剝離及除去 為不必要之光阻圖案之狀態下之實施形態。 圖1係顯示藉由本實施形態所造成之曝光用光罩之製 步驟。 首先，準備在基板上形成作為應該轉印於被轉印體（ 如半導體基板）之轉印圖案之薄膜（例如遮光膜）之光 毛胚（S11)。 在本發明之所謂光罩毛胚係也指透過型光罩毛胚、反 型光罩毛胚之任何一種，這些構造係在基板上，具有對 312XP/發明說明書(補件)/94-07/94109303 顯 成 處 之 漬 呈 影 罩 以 案 9 成 造 例 罩 射 於 18200537258 (N a 0 Η), potassium hydroxide (K 0 Η) and other alkaline substances as the main component of the film. These developer systems are not used in the fire control law or various environmental laws. Therefore, no special management is required to make management easier. In addition, the method of contacting the developing solution in this state is not particularly limited. For example, a method of immersing a substrate having a photoresist film in the developing solution or a substrate having a photoresist film can be arbitrarily selected. The method of supplying the developing solution in a shower-like manner, or the method of blowing the developing solution by spraying, and the like. (Embodiment 2) In Embodiment 2 of the present invention, a predetermined positive photoresist pattern is formed on a photomask blank of a film that is used to transfer a light pattern on a substrate, and the photoresist pattern is etched as a photomask. The exposed film is subjected to a patterning step, and after the remaining photoresist pattern is exposed, the photoresist pattern is manufactured by exposing and removing the photoresist pattern by contacting with a developing solution. This embodiment is an embodiment in a state in which the photoresist pattern is peeled off and removed in the manufacturing steps of an exposure mask. Fig. 1 shows the manufacturing steps of an exposure mask made by this embodiment. First, a light blank (S11) is formed on a substrate as a film (for example, a light-shielding film) that is a transfer pattern that should be transferred to a transfer target (such as a semiconductor substrate). In the present invention, the so-called photomask germ line also refers to any one of a transmissive photomask germ and a reverse photomask germ. These structures are on a substrate and have a pair of 312XP / Invention Specification (Supplement) / 94-07 / 94109303 The stain on the display is a shadow mask. The case is 9%. The mask is shot at 18.
200537258 曝光用光造成化學變化而成為應該轉印於被轉印體之 圖案之薄膜。 透過型光罩毛胚係使用玻璃基板等之透光型基板， 為基板。所謂對於曝光用光來造成化學變化者係指遮 光用光之遮光膜、改變曝光用光之相位之相位移膜（ 位移膜、包含具有遮光功能和相位移功能之半色調膜 因此，透過型光罩毛胚係包含：形成遮光膜之光罩毛 形成相位移膜（包含半色調膜）之相位移光罩毛胚等 仍然，除此之外，也知道有：液晶顯示裝置之製造 用之在基板上形成遮光部、半透光部及透光部之灰色 罩；也包含在成為該灰色調光罩製造之原版、例如基 形成半透光膜和遮光膜之光罩毛胚。 此外，反射型光罩毛胚係使用熱膨脹係數小者，來 基板，成為在該基板上具有光反射多層膜及成為轉印 之光吸收體膜的光罩毛胚。所謂對於該狀態下之曝光 來造成光學變化者係指反射曝光用光之光反射多層膜 斷曝光用光之光吸收體膜等。 這些光罩毛胚（附有薄膜之基板）係藉由在基板上 用濺鍍法或蒸鍍法、C V D法等而形成作為應該轉印於； 印體之轉印圖案之薄膜所製造。 接著，在該光罩毛胚上之整個面，形成正型光阻膜 (S 1 2 )。正型光阻膜之形成係藉由將使得正型光阻材 解於溶媒來調製成為適當黏度之光阻塗敷液而塗敷於 毛胚上之所進行。通常在光阻膜塗敷於光罩毛胚上之 312XP/發明說明書(補件)/94-07/94 ] 09303 轉印 來作 斷曝 在相 )等。 胚、 〇 所使 調光 板上 作為 圖案 用光 和遮 ，利 丨皮轉 料溶 光罩 後， 19 200537258 進行加熱處理（預烘烤）。 接著，藉由在附有該正型光阻膜之光罩毛胚，進行既定 之圖案描繪（曝光）（S 1 3 )，使用顯影液，來進行顯影處理 (S14)，而在光罩毛胚上，形成光阻圖案。在形成光阻圖 案時之曝光係通常是藉由具有單波長之雷射光源之雷射描 繪裝置所造成之掃描曝光。200537258 Exposure light causes chemical changes to form a film that should be transferred to the transferred object. The transmissive photomask blank uses a translucent substrate such as a glass substrate as the substrate. The term “chemical change to light for exposure” refers to a light-shielding film for light-shielding light, and a phase shift film (shift film, which includes a half-tone film with light-shielding function and phase-shift function) for changing the phase of light for exposure. The mask hair embryo system includes: a mask hair that forms a light-shielding film, a phase shift mask hair embryo that forms a phase shift film (including a half-tone film), etc. In addition, it is also known that: the manufacturing of liquid crystal display devices is used in A gray cover of a light-shielding portion, a semi-light-transmitting portion, and a light-transmitting portion is formed on the substrate; it is also included in the original version of the gray light-shielding cover, such as a mask blank that forms a translucent film and a light-shielding film. The type photomask blank uses a substrate with a small thermal expansion coefficient to form a photomask blank having a light reflecting multilayer film and a transferred light absorber film on the substrate. The exposure in this state causes optical The changers refer to the light of the reflective exposure light, the light absorber film of the multilayer exposure film, and the light absorber film of the exposure light, etc. These mask blanks (substrates with a thin film) are formed by sputtering or vapor deposition on the substrate. And a CVD method, etc., which are formed as a film to be transferred to a printed body. Next, a positive photoresist film (S 1 2) is formed on the entire surface of the mask blank. Positive type The photoresist film is formed by dissolving a positive photoresist material in a solvent to prepare a photoresist coating solution of an appropriate viscosity, and applying the photoresist on the hair embryo. Usually, the photoresist film is applied to a photomask. 312XP / Invention Manual (Supplement) / 94-07 / 94] 09303 on hair embryos, etc. The embryo and the light control board used as the pattern are used as a pattern to light and cover, and the skin is converted into a photomask, and then the heat treatment (pre-baking) is performed. Next, a predetermined pattern drawing (exposure) is performed on the photomask blank with the positive-type photoresist film attached (S 1 3), and a developing solution is used to perform a development process (S14). On the embryo, a photoresist pattern is formed. The exposure when forming a photoresist pattern is usually a scanning exposure by a laser drawing device having a laser light source with a single wavelength.
接著，以該光阻圖案作為光罩，藉由蝕刻而除去露出之 薄膜，使得薄膜形成為圖案狀（S 1 5 )。在反射型光罩之狀 態下，使得最上層之光吸收體膜形成為圖案狀。 像這樣，完成在基板上使得薄膜形成為既定之圖案狀之 曝光用光罩。 成為不必要之光阻圖案係相同於上述之實施形態，施行 曝光步驟（S 1 6 )及藉由顯影液所造成之處理步驟（s 1 7 ) 而進行剝離及除去。此時，適合再度實施在上述之光罩毛 胚上形成既定之光阻圖案時之顯影步驟，使得曝光後之殘 留之光阻圖案，接觸到顯影液。由於可以藉此而在圖案化 之光步驟作業中，應付光阻之剝離，能夠達到步驟上之簡 便化之緣故。此外，也並無需要特別地設置光阻剝離步驟 用之生產線，也能夠進行在設備面之簡化。此外，最好是 使用在形成光阻圖案時之顯影手段，使得曝光後之殘留之 光阻圖案，接觸到顯影液。 但是，用以剝離及除去光阻圖案所施行之曝光條件（曝 光波長、曝光量、曝光方法等）以及顯影條件（顯影液之 種類、顯影時間、顯影方法等）係可以相同、也可以不同 20 3 ] 2XP/發明說明書(補件)/94·07/94109303 200537258 於形成光阻圖案時之曝光條件及顯影條件。用以剝離及除 去光阻圖案所施行之曝光條件及顯影條件係也不一定需要 嚴密地設定在形成光阻圖案時之曝光條件及顯影條件。Next, using the photoresist pattern as a photomask, the exposed thin film is removed by etching, so that the thin film is formed into a pattern (S 1 5). In the state of the reflective mask, the uppermost light absorber film is formed into a pattern. In this manner, an exposure mask for forming a thin film into a predetermined pattern on a substrate is completed. The unnecessary photoresist pattern is the same as the above-mentioned embodiment, and is subjected to an exposing step (S 1 6) and a processing step (s 1 7) caused by a developing solution to perform peeling and removal. At this time, it is suitable to perform the development step again when the predetermined photoresist pattern is formed on the mask blank, so that the remaining photoresist pattern after exposure contacts the developing solution. Because this can be used in the patterned light step operation, the peeling of the photoresist can be dealt with, which can achieve the simplicity of the step. In addition, there is no special production line for the photoresist stripping step, and the equipment can be simplified. In addition, it is preferable to use a developing means when forming the photoresist pattern so that the photoresist pattern remaining after exposure contacts the developing solution. However, the exposure conditions (exposure wavelength, exposure amount, exposure method, etc.) and development conditions (type of developer, development time, development method, etc.) used to peel and remove the photoresist pattern may be the same or different. 3] 2XP / Invention Manual (Supplement) / 94 · 07/94109303 200537258 Exposure and development conditions when forming a photoresist pattern. The exposure conditions and development conditions for peeling and removing the photoresist pattern do not necessarily need to be set strictly under the exposure conditions and development conditions when forming the photoresist pattern.
此外，曝光量係以光阻之剝離，作為目的，因此，最好 是比起通常之光阻圖案之形成所需要之曝光量，還賦予更 多（例如2倍以上）之曝光量。在基板上具有鉻（C r )遮 光膜之光罩製造之狀態下，由於鉻之濕式蝕刻所使用之蝕 刻液（一般是二代鈽硝酸銨和過氣酸）而改質光阻圖案之 表面，不容易藉由曝光而進行感光，因此，藉由增加曝光 量，來賦予強能量，而使得光阻圖案之剝離除去，變得容 易。 此外，在剝離及除去光阻圖案之狀態下之顯影方法係以 來自基板之光阻剝離，作為目的，因此，可以一次處理許 多片，也能夠以聯機方式，來連續地進行處理。 此外，在本發明之實施形態，可以藉由在光阻圖案之剝 離除去之所使用之顯影裝置，附設曝光手段，而在相同裝 置内，連續地進行包含曝光及藉由顯影液所造成之處理之 光阻圖案之剝離除去步驟。此外，可以藉由並設顯影裝置 和曝光裝置，藉由並設包含曝光及藉由顯影液所造成之處 理之光阻圖案之剝離除去步驟之裝置間之搬送而連續地進 行。 (實施形態3 ) 本發明之實施形態3係一種光阻剝離裝置，係用以藉由 在對於具有正型光阻膜之基板之光阻膜面來進行曝光後， 21 312XP/發明說明書(補件)/94-07/94109303 200537258 使得曝光之光阻膜，接觸到溶解曝光之光阻之處理液’而 由上述基板，來剝離及除去正型光阻膜的光阻剝離裝置， 具有：具有保持上述基板之保持手段和對向於上述基板之 光阻膜面所設置之光照射手段的曝光室；具有保持上述基 板之保持手段和在上述基板之光阻膜面將溶解曝光之光阻 之處理液予以供應之處理液供應手段並且剝離及除去曝光 之光阻的處理室；以及，將上述基板由上述曝光室開始搬 送至上述處理室的基板搬送手段。In addition, the exposure amount is for the purpose of peeling off the photoresist. Therefore, it is better to give more (for example, 2 times or more) the exposure amount than that required for the formation of a normal photoresist pattern. In the state of manufacturing a photomask with a chromium (Cr) light-shielding film on the substrate, the photoresist pattern is modified due to the etching solution used for wet etching of chromium (generally ammonium nitrate and peroxyacid). It is not easy to perform photosensitivity on the surface by exposure. Therefore, by increasing the amount of exposure, strong energy is provided, and peeling and removal of the photoresist pattern becomes easy. In addition, the development method in the state of peeling and removing the photoresist pattern is for the purpose of peeling off the photoresist from the substrate, and therefore, it is possible to process many pieces at a time or to perform continuous processing in an in-line manner. In addition, in the embodiment of the present invention, the developing device used for peeling and removing the photoresist pattern can be provided with an exposure means, and in the same device, processes including exposure and processing by a developing solution can be continuously performed. Step of removing the photoresist pattern. In addition, the development device and the exposure device may be arranged in parallel, and the transfer between the devices including the peeling and removing steps of the photoresist pattern including the exposure and the treatment by the developer may be performed in parallel. (Embodiment 3) Embodiment 3 of the present invention is a photoresist peeling device for exposing the photoresist film surface of a substrate having a positive photoresist film. 21 312XP / Invention Specification (Supplement Pieces) / 94-07 / 94109303 200537258 A photoresist peeling device for exposing and removing a positive type photoresist film from the above substrate by contacting the exposed photoresist film with a processing solution that dissolves the exposed photoresist. An exposure chamber for holding the substrate and a light irradiating means provided to the photoresist film surface of the substrate; a holding device for holding the substrate and a photoresist for dissolving and exposing the photoresist film on the substrate A processing liquid supply means for supplying the processing liquid and a processing chamber for peeling and removing the exposed photoresist; and a substrate transfer means for transferring the substrate from the exposure chamber to the processing chamber.
圖3係本實施形態之光阻剝離裝置之前視圖，圖4係本 實施形態之光阻剝離裝置之裝料器/卸料器室之側剖面 圖，圖5係本實施形態之光阻剝離裝置之曝光室之側剖面 圖，圖6係本實施形態之光阻剝離裝置之處理室之側剖面 圖0 正如圖4至圖6所示，本實施形態之光阻剝離裝置1係 各個室傾斜成為既定之角度α，而使得基板2 0之主表面能 夠進行傾斜及保持，來朝向斜上方。 此外，正如圖3所示，光阻剝離裝置1係由圖中之右邊 開始，併設裝料器/卸料器室2、曝光室3、處理室4。此 外，沿著各個室之背面，在上下之方向，以概略一定之間 隔，來配置許多之支持用輥子1 2。各個支持用輥子1 2係 可自由旋轉地軸承於配置在上下方向之保持軸1 3。此外， 沿著背面，也在左右之方向，以相同之構造，來配置許多 之支持用輥子1 2。藉此而使得各個支持用輥子1 2，以平行 於上述背面1 Β之平行之保持軸1 3作為中心而成為自由旋 22 312ΧΡ/發明說明書(補件)/94-07/94】09303 200537258FIG. 3 is a front view of the photoresist peeling device of this embodiment, FIG. 4 is a side sectional view of a loader / unloader chamber of the photoresist peeling device of this embodiment, and FIG. 5 is a photoresist peeling device of this embodiment FIG. 6 is a side sectional view of a processing chamber of the photoresist peeling apparatus of this embodiment. As shown in FIGS. 4 to 6, each of the photoresist peeling apparatuses of this embodiment is tilted into The predetermined angle α enables the main surface of the substrate 20 to be tilted and held to face obliquely upward. In addition, as shown in FIG. 3, the photoresist peeling device 1 is started from the right side in the figure, and a loader / unloader chamber 2, an exposure chamber 3, and a processing chamber 4 are provided. In addition, a plurality of support rollers 12 are arranged along the back surface of each chamber at a substantially constant interval in the up-down direction. Each of the supporting rollers 12 and 2 is rotatably supported on a holding shaft 13 arranged in the vertical direction. In addition, a plurality of supporting rollers 12 are arranged along the back side and in the left-right direction with the same structure. As a result, each supporting roller 12 becomes a free-spinning centered on a parallel holding axis 1 3 parallel to the above-mentioned back surface 1 B 22 312XP / Invention Specification (Supplement) / 94-07 / 94] 09303 200537258
轉。像這樣，在沿著各個室之内部之背面1 B所配置之許多 之支持用輥子1 2上載置基板2 0時，基板2 0之背面（相反 於主表面之相反側之面、也就是相反於光阻膜面之相反側 之面）接於各個支持用輥子1 2之周圍面，因此，基板 2 0係可以在由裝料器/卸料器室2開始折回至曝光室3、 由曝光室3開始折回至處理室4、由處理室4開始折回而 搬入及搬出至裝料器/卸料器室2之左右方向之搬入搬出 時，進行移動（滑動）。此外，可以藉由在基板2 0之下端， 配置以垂直於上述背面1B之垂直方向之軸作為中心來自 由地進行旋轉之搬送用輥子1 4，支持基板2 0之下端來抵 接於設置在該搬送用輥子1 4周圍面之保持溝槽1 4 A，藉由 旋轉上述搬送用輥子1 4，而使得基板2 0移動至左右方向。 像這樣，成為支持著基板2 0下端之構造，因此，可以使用 在對於不同尺寸之基板。 接著，就各個室而言，詳細地進行說明。 正如圖4所示，裝料器/卸料器室2係成為開放正面1 A 側之箱型形狀而能夠進出於載置在搬送用輥子1 4之基板 20 0 接著，正如圖5所示，鄰接於裝料器/卸料器室2之曝 光室3係在面對著正面1 A側之基板2 0表面之内壁面，具 有紫外線燈等之光照射手段1 5。 接著，正如圖6所示，鄰接於曝光室3之處理室4係配 置能夠對於基板2 0之某一邊方向（在本實施形態、成為基 板2 0傾斜方向之上下（縱）方向）呈概略均等地供應處理 23 312XP/發明說明書(補件)/94-07/94109303 200537258turn. In this way, when the substrate 20 is placed on many supporting rollers 12 arranged along the back surface 1 B inside each chamber, the back surface of the substrate 20 (the opposite side to the main surface, that is, the opposite direction) The surface on the opposite side of the photoresist film surface) is connected to the surrounding surface of each supporting roller 12. Therefore, the substrate 20 can be folded back from the loader / unloader chamber 2 to the exposure chamber 3, and exposed by exposure. The chamber 3 starts to be folded back to the processing chamber 4, and is moved (slided) when being moved in and out to the loader / unloader chamber 2 in the left-right direction when the processing chamber 4 starts to be folded back. In addition, the lower end of the substrate 20 may be provided with a transfer roller 14 which rotates freely around an axis perpendicular to the back surface 1B as a center, and the lower end of the support substrate 20 may abut on the The holding grooves 14A on the peripheral surface of the transfer roller 14 are rotated to move the substrate 20 to the left-right direction by rotating the transfer roller 14 described above. Since it has a structure supporting the lower end of the substrate 20, it can be used for substrates of different sizes. Next, each room will be described in detail. As shown in FIG. 4, the loader / unloader chamber 2 has a box shape with an open front 1 A side and can be inserted into and out of a substrate 20 0 placed on a transport roller 14. Next, as shown in FIG. 5, The exposure chamber 3 adjacent to the loader / unloader chamber 2 is on the inner wall surface of the surface of the substrate 20 facing the 1 A side of the front surface, and has light irradiation means 15 such as an ultraviolet lamp. Next, as shown in FIG. 6, the processing chamber 4 adjacent to the exposure chamber 3 is arranged so as to be roughly equal to one side direction of the substrate 20 (in this embodiment, the substrate 20 is tilted up and down (longitudinal)). Ground Supply Processing 23 312XP / Invention Specification (Supplement) / 94-07 / 94109303 200537258
液之噴射嘴3 0 (參考圖3 )，來作為上述處理液供應手段。 此外，該喷射嘴3 0係保持既定之間隔，呈平行地配置在基 板20之主表面上，使得直交於上述某一邊方向之基板主表 面上、也就是在本實施形態之基板主表面上，進行掃描至 左右方向（記載於圖3中之箭號之方向）之掃描（scan) 動作。該喷射嘴3 0係整體形成為管狀，在其表面，沿著長 邊方向，在概略相等之間隔，具有複數個噴嘴孔3 1 (參考 圖6。此外，在圖6，為了方便起見，省略喷嘴30之圖示。）， 在喷射嘴3 0以既定之水壓來供應處理液、例如顯影液時， 由喷射嘴3 0之各個喷嘴孔3 1開始，呈淋浴狀地喷出顯影 液。在本實施形態，跨越基板2 0之上下方向而配置喷射嘴 30來成為長邊方向，因此，能夠對於基板20之上下方向， 呈概略均等地供應處理液。接著，可以藉由使得噴射嘴3 0 掃描於基板20之主表面上至左右方向，而在基板20主表 面之整個區域，呈概略均等地充滿處理液。 接著，就使用本實施形態之光阻剝離裝置1而剝離光阻 之順序，來進行說明。首先，在裝料器/卸料器室2之搬 送用輥子1 4，載置具有剝離之光阻膜之基板2 0。接著，以 一定之速度來旋轉搬送用輥子14，以一定之速度來傳送及 通過基板2 0至曝光室3。此時，曝光室3之光照射手段1 5 係成為電源導通之狀態。通過曝光室3之基板2 0係接著搬 送至處理室4而停止。接著，藉由使用喷射嘴3 0，供應處 理液至基板2 0之整個面，而剝離及除去光阻。此外，使用 噴射嘴3 0，供應純水至基板2 0之整個面而進行漂洗。然 24 312XP/發明說明書(補件)/94-07/94109303 200537258 後，對於搬送用輥子1 4進行逆旋轉，沿著裝料器/卸料器 室2之方向，來移動基板2 0，通過光照射手段1 5之電源 成為OFF (斷開）狀態之曝光室3，搬送至裝料器/卸料器 室2，在停止後，取出基板2 0。可以藉由此種順序而連續 地進行對於光阻膜之光照射以及由於處理液所造成之處 理 。The liquid spray nozzle 30 (refer to FIG. 3) is used as the processing liquid supply means. In addition, the spray nozzles 30 are arranged at a predetermined interval on the main surface of the substrate 20 in parallel so as to be orthogonal to the main surface of the substrate in one of the above-mentioned directions, that is, on the main surface of the substrate in this embodiment. Scan to the left and right direction (the direction indicated by the arrow in Figure 3). The injection nozzle 30 is formed into a tubular shape as a whole, and has a plurality of nozzle holes 3 1 (see FIG. 6) at roughly equal intervals along the longitudinal direction on the surface thereof. In addition, in FIG. 6, for convenience, The illustration of the nozzle 30 is omitted.), When the injection nozzle 30 supplies a processing liquid such as a developing solution at a predetermined water pressure, the developing solution is ejected from each nozzle hole 31 of the injection nozzle 30 in a shower shape. . In this embodiment, since the spray nozzles 30 are arranged across the substrate 20 in the up-down direction to form the long side direction, the processing liquid can be supplied roughly uniformly in the up-down direction of the substrate 20. Then, the nozzle 30 can be scanned from the main surface of the substrate 20 to the left-right direction, and the entire area of the main surface of the substrate 20 can be filled with the processing liquid roughly uniformly. Next, a procedure for removing the photoresist using the photoresist peeling device 1 of this embodiment will be described. First, on the transfer roller 14 of the loader / unloader chamber 2, a substrate 20 having a peeled photoresist film is placed. Next, the conveyance roller 14 is rotated at a constant speed, and is conveyed and passed through the substrate 20 to the exposure chamber 3 at a constant speed. At this time, the light irradiation means 15 of the exposure chamber 3 is in a state where the power source is turned on. The substrate 20 passing through the exposure chamber 3 is then transferred to the processing chamber 4 and stopped. Next, by using the spray nozzle 30, the processing liquid is supplied to the entire surface of the substrate 20, and the photoresist is peeled off and removed. In addition, the spray nozzle 30 was used to supply pure water to the entire surface of the substrate 20 to perform rinsing. After 24 312XP / Invention Specification (Supplement) / 94-07 / 94109303 200537258, the conveying roller 14 is reversely rotated, and the substrate 20 is moved in the direction of the loader / unloader chamber 2 to pass the light. The exposure chamber 3, in which the power of the irradiation means 15 is turned OFF, is transferred to the loader / unloader chamber 2, and after stopping, the substrate 20 is taken out. In this order, light irradiation to the photoresist film and processing caused by the treatment liquid can be performed continuously.
如果藉由本實施形態之光阻剝離裝置1的話，則可以藉 由即使是對於大型基板，也使得傾斜角度變大，而達到省 空間化。在參考圖4至圖6時而得知：在本實施形態之光 阻剝離裝置1之狀態下，裝置之深度（D )係變得更加小於 基板尺寸。由該觀點來看的話，則正如前面敘述，特別是 對於大型基板而使得基板之傾斜角度適合成為2 5度以 上、更加理想是4 5度以上。此外，即使是由於基板之傾斜 角度變大而使得處理液之流落速度變快，也可以藉由能夠 供應處理液至基板主表面之整個區域而進行高處理能力並 且高均勻性之處理。因此，本發明之光阻剝離裝置係特別 適合於進行至少一邊之長度成為300mm以上之大型基板之 光阻剝離之狀態。也就是說，即使是對於大型基板，也可 以進行省空間化、高處理能力並且高均勻性之光阻剝離處 理 。 此外，在上述實施形態，分別使得裝料器/卸料器室2 和曝光室3、曝光室3和處理室4進行鄰接及配置，但是， 也可以分別將具有其他功能之部分，配置於其間。例如可 以在曝光室3和處理室4之間，設置供應氣體之乾燥室， 25 312XP/發明說明書(補件)/94-07/94109303 200537258 來乾燥顯影漂洗後之基板。此外，可以在各個室，兼備其 他功能。 以下，藉由實施例而更加具體地說明本發明之實施形 (實施例1 ) 在基板尺寸330mmx450nim之合成石英玻璃基板上，藉由 濺鍍法而依序地疊層鉻膜和氧化鉻膜，得到在基板上形成 遮光膜和反射防止膜之液晶顯示裝置製造用之光罩毛胚。If the photoresist peeling device 1 according to this embodiment is used, the inclination angle can be increased even for a large substrate, and space saving can be achieved. When referring to FIG. 4 to FIG. 6, it is known that in the state of the photoresist peeling device 1 of this embodiment, the depth (D) of the device becomes smaller than the substrate size. From this point of view, as described above, particularly for large substrates, the inclination angle of the substrate is preferably 25 degrees or more, and more preferably 45 degrees or more. In addition, even if the flow rate of the processing liquid is increased due to the increase in the tilt angle of the substrate, it is possible to perform processing with high processing capacity and high uniformity by supplying the processing liquid to the entire area of the main surface of the substrate. Therefore, the photoresist peeling device of the present invention is particularly suitable for the state where the photoresist is peeled off from a large substrate having a length of at least one side of 300 mm or more. That is, even for large substrates, it is possible to perform a photoresist peeling process that saves space, has high processing capacity, and has high uniformity. In addition, in the above-mentioned embodiment, the loader / unloader chamber 2 and the exposure chamber 3, the exposure chamber 3, and the processing chamber 4 are adjacent and arranged, respectively. However, parts having other functions may be arranged therebetween. . For example, a drying chamber for supplying gas may be provided between the exposure chamber 3 and the processing chamber 4, 25 312XP / Invention Specification (Supplement) / 94-07 / 94109303 200537258 to dry the developed and rinsed substrate. In addition, other functions can be combined in each room. Hereinafter, the embodiment of the present invention (Example 1) will be described in more detail by way of examples. On a synthetic quartz glass substrate having a substrate size of 330 mmx450 nm, a chromium film and a chromium oxide film are sequentially laminated by a sputtering method. A photomask blank for manufacturing a liquid crystal display device in which a light-shielding film and an anti-reflection film are formed on a substrate is obtained.
在得到之光罩毛胚上，使用旋轉器（旋轉塗敷裝置）， 對於正型光阻液進行旋轉及塗敷，形成正型光阻膜。作為 正型光阻係使用高分子量型光阻P B S (聚丁烯一1 一颯）， 以將這個溶解於甲基乙二醇乙醚乙酸酯者，來作為光阻 液。此外，在塗敷上述光阻液後，使用加熱乾燥裝置，來 進行既定之加熱乾燥處理。 接著，對於附有正型光阻膜之光罩毛胚，進行藉由曝光 裝置（雷射描繪裝置）所造成之曝光，然後，進行藉由以 氫氧化鉀（K 0 Η )作為主成分之顯影液所造成之顯影處理， 在光罩毛胚上，形成既定之光阻圖案。此外，上述顯影處 理係進行於2 3 °C、6 0秒鐘。 接著，以上述光阻圖案作為光罩，藉由濕式蝕刻處理而 除去露出之氧化鉻膜及鉻膜，在基板上，呈既定圖案狀地 形成鉻遮光膜及反射防止膜。蝕刻液係使用二代鈽硝酸銨 和過氣酸之水溶液。 接著，為了剝離及除去殘留之光阻圖案，因此，進行曝 26 312XP/發明說明書(補件)/94-07/94109303On the obtained photomask blank, a spinner (spin coating device) was used to spin and coat the positive photoresist liquid to form a positive photoresist film. As the positive type photoresist system, a high molecular weight type photoresist P B S (polybutene-1 1 飒) was used, and this was dissolved in methyl ethylene glycol ether acetate as a photoresist solution. After applying the photoresist liquid, a predetermined heating and drying process is performed using a heating and drying device. Next, for the photomask blank with a positive photoresist film, exposure was performed by an exposure device (laser drawing device), and then, it was performed by using potassium hydroxide (K 0 Η) as a main component. The developing process caused by the developing solution forms a predetermined photoresist pattern on the photomask blank. In addition, the above-mentioned developing process was performed at 2 3 ° C and 60 seconds. Next, using the photoresist pattern as a photomask, the exposed chromium oxide film and chromium film are removed by a wet etching process, and a chromium light-shielding film and an anti-reflection film are formed on the substrate in a predetermined pattern. As the etching solution, an aqueous solution of ammonium nitrate of second generation and peroxyacid is used. Next, in order to peel off and remove the remaining photoresist pattern, exposure was performed 26 312XP / Invention Specification (Supplement) / 94-07 / 94109303
200537258 光處理以及藉由顯影液所造成之處理。該狀態下之曝 理係使用以水銀燈作為光源之曝光裝置而進行全面曝 由於認為藉由上述蝕刻液而改質光阻圖案之表面，因 設定曝光時間變長而更加多於通常之光阻圖案形成所 之曝光量。此外，藉由顯影液所造成之處理係以概略 於上述光阻圖案形成時之顯影之條件來進行。像這樣 以藉由進行曝光處理以及使用顯影液之處理而剝離及 殘留之光阻圖案。 正如以上，得到在玻璃基板上具有形成為既定之圖 之鉻遮光膜和反射防止膜之透過型曝光用光罩（液晶 裝置製造用之大型光罩）。 (實施例2 ) 在相同於實施例1所製作之液晶顯示裝置製造用之 光罩毛胚上，使用C A P塗敷器而進行光阻之塗敷。在 施例所使用之CAP塗敷器係具體地成為圖7所示之裝 藉由在利用光阻液41所充滿之液槽4 2之内告卩，沉降 毛細管狀間隙W之噴嘴4 3，上升喷嘴4 3，而位處在使 表面朝向於下方之基板40之主表面附近，由毛細管狀 W開始，使用毛細管現象，使得上升至喷嘴4 3尖端之 液41，接觸到基板4 0之主表面，同時，使得基板4 0 至圖示之箭號方向，在基板40之表面，塗敷光阻膜。 用此種塗敷方法之狀態下，在基板之側面或背面，並 轉入光阻而進行塗敷，因此，可以適當地使用本發明 阻剝離方法。 3 ] 2XP/發明說明書(補件)/9‘07/94109303 光處 光。 此， 需要 相同 ，可 除去 案狀 顯示 大型 本實 置， 具備 得主 間隙 光阻 移動 在使 無旋 之光 27 200537258 接著，對於該附有正型光阻膜之光罩毛胚，相同於實施 例1，形成既定之光阻圖案，以該光阻圖案作為光罩，對 於氧化鉻膜及鉻膜，進行蝕刻處理，在基板上，呈既定圖 案狀地形成鉻遮光膜及反射防止膜。200537258 Light processing and processing caused by the developer. The exposure in this state is a full exposure using an exposure device using a mercury lamp as a light source. It is considered that the surface of the photoresist pattern is modified by the above-mentioned etching solution, and because the exposure time is set longer, it is more than the ordinary photoresist pattern. The amount of exposure is formed. In addition, the treatment by the developing solution is performed under conditions that are roughly similar to the development conditions when the photoresist pattern is formed. In this manner, a photoresist pattern that is peeled off and left by performing an exposure process and a process using a developer is performed. As described above, a transparent photomask (a large photomask for the manufacture of a liquid crystal device) having a chromium light-shielding film and an anti-reflection film formed on a glass substrate in a predetermined pattern was obtained. (Example 2) A photoresist was applied to a mask blank for manufacturing a liquid crystal display device prepared in the same manner as in Example 1, using a CAP applicator. The CAP applicator used in the embodiment is specifically a nozzle 4 3 as shown in FIG. 7 by sinking the capillary gap W in the liquid tank 42 filled with the photoresist liquid 41, The nozzle 4 3 is raised, and is located near the main surface of the substrate 40 with the surface facing downward, starting from a capillary W, using a capillary phenomenon, so that the liquid 41 rising to the tip of the nozzle 4 3 contacts the main body of the substrate 40 At the same time, a photoresist film is coated on the surface of the substrate 40 such that the substrate 40 goes to the arrow direction shown in the figure. In such a coating method, a photoresist is applied to the side or back of the substrate to perform coating. Therefore, the peeling prevention method of the present invention can be suitably used. 3] 2XP / Invention Manual (Supplement) / 9 '07 / 94109303 Light place Light. Therefore, it is necessary to remove the case and display a large-sized book, and the winner has a gap photoresist to move the light without rotation. 27 200537258 Next, the mask blank with a positive photoresist film is the same as the embodiment. 1. Form a predetermined photoresist pattern, use the photoresist pattern as a photomask, and etch the chromium oxide film and the chromium film, and form a chromium light-shielding film and an anti-reflection film in a predetermined pattern on the substrate.
接著，為了剝離及除去殘留之光阻圖案，因此，使用在 上述實施形態3所說明之光阻剝離裝置。此外，適當地設 定曝光室之曝光條件，在處理室所供應之處理液係使用在 光阻圖案形成時之顯影液。像這樣，可以藉由使用光阻剝 離裝置，連續地進行對於光阻圖案之光照射以及使用顯影 液之處理，而剝離及除去殘留之光阻圖案。 正如以上，得到在玻璃基板上具有形成為既定之圖案狀 之鉻遮光膜和反射防止膜之透過型曝光用光罩（液晶顯示 裝置製造用之大型光罩）。 此外，在以上之實施例，顯示在透過型曝光用光罩之某 一例子之製造步驟而實施藉由本發明所造成之正型光阻膜 之剝離除去之狀態，但是，當然本發明係並非限定於該實 施例。例如即使是在上述相位移光罩、灰色調光罩或反射 型曝光用光罩之製造步驟，也可以藉由本發明而剝離及除 去正型光阻膜。此外，雖然並無顯示在實施例，但是，即 使是在半導體裝置或液晶顯示裝置之製造步驟，也可以藉 由本發明而剝離及除去隨著微影步驟所帶來之殘留之正型 光阻膜。 【圖式簡單說明】 圖1係顯示藉由本發明所造成之曝光用光罩之製造步驟 28 3 ] 2XP/發明說明書(補件)/94-07/94109303 200537258 之圖。 圖2係顯示習知之曝光用光罩之製造步驟之圖。 圖3係本發明之某一實施形態之光阻剝離裝置之前視 圖。 圖4係本發明之某一實施形態之光阻剝離裝置之裝料器 /卸料器室之側剖面圖。 圖5係本發明之某一實施形態之光阻剝離裝置之曝光室 之側剖面圖。Next, in order to peel off and remove the remaining photoresist pattern, the photoresist peeling device described in the third embodiment is used. In addition, the exposure conditions of the exposure chamber are appropriately set, and the processing solution supplied in the processing chamber is a developing solution used when the photoresist pattern is formed. In this manner, by using a photoresist stripping device, the photoresist pattern can be continuously irradiated with light and a treatment using a developing solution can be performed to remove and remove the remaining photoresist pattern. As described above, a transmission type photomask (a large photomask for manufacturing a liquid crystal display device) having a chromium light-shielding film and an anti-reflection film formed in a predetermined pattern on a glass substrate is obtained. In addition, in the above embodiment, the state in which the positive-type photoresist film was peeled and removed by the manufacturing steps of an example of a transmission-type exposure mask was shown, but the present invention is not limited thereto, of course.于此 实施 例。 In this embodiment. For example, the positive-type photoresist film can be peeled off and removed by the present invention even in the manufacturing steps of the phase shift mask, the gray mask, or the reflective exposure mask. In addition, although it is not shown in the embodiment, even in the manufacturing steps of a semiconductor device or a liquid crystal display device, the present invention can be used to peel off and remove the residual positive photoresist film caused by the lithography step. . [Brief description of the drawings] FIG. 1 is a diagram showing the manufacturing steps of an exposure mask caused by the present invention. 28 3] 2XP / Invention Specification (Supplement) / 94-07 / 94109303 200537258. FIG. 2 is a diagram showing the manufacturing steps of a conventional exposure mask. Fig. 3 is a front view of a photoresist peeling device according to an embodiment of the present invention. Fig. 4 is a side sectional view of a loader / unloader chamber of a photoresist peeling device according to an embodiment of the present invention. Fig. 5 is a side sectional view of an exposure chamber of a photoresist peeling apparatus according to an embodiment of the present invention.
圖6係本發明之某一實施形態之光阻剝離裝置之處理室 之側剖面圖。 圖7係CAP塗敷器之模式構成圖。 【主要元件符號說明】 a 角度 D 深度 W 毛細管狀間隙Fig. 6 is a side sectional view of a processing chamber of a photoresist peeling apparatus according to an embodiment of the present invention. Fig. 7 is a schematic configuration diagram of a CAP applicator. [Description of main component symbols] a Angle D Depth W Capillary gap
1 A 正面 1 B 背面 2 裝料器/卸料器室 3 曝光室 4 處理室 12 支持用輥子 13 保持軸 14 搬送用輥子 29 312XP/發明說明書(補件)/94-07/94109303 200537258 1 4 A 15 20 30 31 40 411 A front 1 B back 2 loader / unloader chamber 3 exposure chamber 4 processing chamber 12 support roller 13 holding shaft 14 transport roller 29 312XP / Invention Manual (Supplement) / 94-07 / 94109303 200537258 1 4 A 15 20 30 31 40 41
42 43 保持溝槽 光照射手段 基板 喷射嘴 喷嘴孔 基板 光阻液 液槽 喷嘴42 43 Holding groove Light irradiation means Substrate Nozzle Nozzle hole Substrate Photoresist liquid tank Nozzle
312XP/發明說明書(補件)/94-07/94〗09303312XP / Invention Specification (Supplement) / 94-07 / 94〗 09303
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| JP2004097077 | 2004-03-29 | ||
| JP2005069133A JP2005317929A (en) | 2004-03-29 | 2005-03-11 | Method of peeling positive resist film, method of manufacturing exposure mask, and resist peeling device |
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| TW200537258A true TW200537258A (en) | 2005-11-16 |
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| JP2007219038A (en) * | 2006-02-15 | 2007-08-30 | Hoya Corp | Mask blank and photomask |
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| JP5363724B2 (en) * | 2007-12-13 | 2013-12-11 | Ｈｏｙａ株式会社 | Photomask blank, photomask, manufacturing method thereof, and coating apparatus |
| JP2009294682A (en) * | 2009-09-24 | 2009-12-17 | Hoya Corp | Mask blank and photomask |
| CN101794089B (en) * | 2010-04-12 | 2012-06-13 | 常州瑞择微电子科技有限公司 | Resist removing method of electron beam resist optical mask plate and device thereof |
| CN104347352B (en) * | 2013-07-31 | 2018-05-29 | 细美事有限公司 | A kind of substrate board treatment and substrate processing method using same |
| CN103399468A (en) * | 2013-08-08 | 2013-11-20 | 深圳市华星光电技术有限公司 | Method and device for stripping photoresist layer |
| CN105045051B (en) * | 2015-08-24 | 2016-06-01 | 北京中科紫鑫科技有限责任公司 | The minimizing technology of photoresist material |
| CN113176703A (en) * | 2021-03-26 | 2021-07-27 | 深圳市路维光电股份有限公司 | Mask stripping and photoresist removing method, manufacturing method and mask |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06164101A (en) * | 1992-11-18 | 1994-06-10 | Nec Ibaraki Ltd | Method for separating photosensitive coating |
| JPH09276773A (en) * | 1996-04-10 | 1997-10-28 | Dainippon Screen Mfg Co Ltd | Substrate treating device |
| JP2000147793A (en) * | 1998-11-12 | 2000-05-26 | Mitsubishi Electric Corp | Method for removing photoresist film and apparatus therefor |
| JP3629386B2 (en) * | 1999-07-23 | 2005-03-16 | 大日本スクリーン製造株式会社 | Substrate processing equipment |
| US6358856B1 (en) * | 2000-11-21 | 2002-03-19 | Advanced Micro Devices, Inc. | Bright field image reversal for contact hole patterning |
| JP3818188B2 (en) * | 2002-03-22 | 2006-09-06 | Ｔｄｋ株式会社 | Mask pattern forming method, patterning method using the mask pattern, and thin film magnetic head manufacturing method |
-
2005
- 2005-03-11 JP JP2005069133A patent/JP2005317929A/en active Pending
- 2005-03-25 TW TW094109303A patent/TW200537258A/en unknown
- 2005-03-29 KR KR1020050026086A patent/KR100680553B1/en not_active IP Right Cessation
- 2005-03-29 CN CNA2005100597013A patent/CN1677247A/en active Pending
Also Published As
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|---|---|
| KR20060044946A (en) | 2006-05-16 |
| CN1677247A (en) | 2005-10-05 |
| JP2005317929A (en) | 2005-11-10 |
| KR100680553B1 (en) | 2007-02-08 |
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