200842492 九、發明說明： 【發明所屬之技術領域】 本案與空自光罩的製造技術有關，更詳而言之，係對其光罩基板進行 保護使其可多次重覆使用之技術，以及關於該基板回收方法。 【先前技術】 在例如結構半導體及TFT元件的製造過程中，一種在時間上較具經濟效 益之微型化電子元件的量^方法，是親—侧案化光罩將其上的圖案轉 移到基板上。圖案化光罩係在—種稱之為空自光罩的表面制_光阻層後 以錯射束或電子束描刻醜喊。如第—圖，空自光罩观常是在玻璃或 石英基板51上鍍製一層很薄的金屬層52(例如鉻、鉬、鎢）。典型的製程包括: 於-玻璃或石英基板Μ上鍍製—層鉻52 ;祕騎％上鑛製_層抗反射層 53以形成一空白之基板(如第一圖）；於抗反射層53上使用一光阻層54 ;在光 阻層54上直寫出一種要求的圖案％(如第二圖）；以鐘射束或電子束於絡攸 餘刻H玄圖案59(如第三圖）；並去除殘留的光阻層。 於鉻層_形成圖案的過程中，石彡基板經過鐳射束或電子束描刻後 易使石英基板表面受損，導致其表面留下圖案的殘影而無法再度使用， 英基板迈>[貝非常昂貴，於一次使用後即報廢將使得圖案化光罩的製造 成本大巾田提昇。於是回收石英基板再加以利用是非常必要的。現有的方式 等土板再研磨’去除上述各層並企圖消除基板上的圖案殘影，但此等以 “再生基板回收使帛之方法，不但料造成基板表面精度降低導致產品 又率曰问，且研磨後基板厚度變薄無法多次回收使用，使回收次數受限， 更因精密研磨之成本極高，實際时效益不大。 200842492 【發明内容】 本案之主要目的係在提出一種使基板得以回收再使用的方案。該方案 -事實上是-種保護基板的措施，在空白光罩製作過程中在金屬層(例如絡、 !目、鎢)及基板表面之_製—層保護材料，以避免基板在瞧化光罩的過 程中留下圖案殘影。並且本案提出回收基板的方案，其包括了去除保護材 料或不去除保護材料。 本案達成上述目的之實施技術，主要係在空白光革製作過程中，於金 離屬層及基板表面之間，鍍製一保護層。該保護層具有高穿透率。 本案所實施的保護層可延長基板的性能穩定度，以及增加基板的再使 用次數。 本案之倾層除了使基板在光罩_化的製程中不受侧影響而留下 殘影之外，光罩在終端客戶使用多次後，可執行本案之脫膜法讓基板可再 度使用。脫膜法可選擇除去或不除去上次使用的保護層。選擇除去保護層， 其實施方案是將光罩浸入一具有可與保護層材料產生侧反應的脫膜液 巾’保護層被賴液侧，因此連帶使保護層上的金屬層、抗反射層、光 阻層等-併脫離基板。選擇不除擁護層，其實施方案是將光罩浸入—具 有可與金屬層材料產魏刻反應的脫膜液中，金屬層被賴祕刻，因此 、吏八上的抗反射層、光阻層—併麟基板，但基板上留下保護層。 【實施方式】 如第四圖，為本案空白光罩實施例截面簡圖。該空白光罩⑺由底部到 、陆夕包括基板11、保濩層、金屬層13(例如鉻、錮、鎢）；一抗反射 200842492 層14可在金屬層13上表面鍍製，也可在金屬層13和保護層12之間鍍製，在 圖式中，該抗反射層14是在金屬層13與光阻層15之間。上述保護層12可以 任何對於鐳射束或電子束有抵抗力的材料實施，廣義而言，它是一種可以 避免光罩圖案化時於基板上產生痕跡的鍍層，其可為抗反射層或高穿透 層。例如，在深紫外線的直寫鐳射光罩製造過程中，一種氟化鎂(MgF〇材料 可用以實現上述之保護層。在本案實施例中，保護層12的折射係數與基板 11的折射係數匹配，以t = A/4n方程式表示，其中t=保護鍍層材料厚度；乂 -光波長，η=保護鍍層材料折射係數。並且保護鍍層最佳的折射係數為 /~nsub。以深紫外線的直寫成像為例，通常保護層材料折射係數約1.79至 1·83。因此，保護層的厚度通常是大約65〇A到大約675A的範圍。並且保護 鑛層的折射係數大約在1·32到1.45的範圍内。 如第五圖，說明本案上述空白光罩直寫圖案的簡圖。圖中顯示了一個 包括上述基板11、保護層12、金屬層13、抗反射層14之空白光罩，及一位 於空白光罩表面之光阻層15的結構1〇〇，上述結構1〇〇曝露於有光化性的輻 射中，使光阻層15產生圖案。在光阻層15產生圖案之後，上述結構卿被設 定在特㈣溫度範_進行熱處理，峨進光阻層ls内充份的化學反應， 使圖案2〇〇傳遞到光阻層b的整個厚度内，使圖案2〇〇正禮地顯影。在圖案 顯影之後，將上述結構!00浸置在顯影劑液體中，利用顯影劑將溶解的光阻 材料15帶離基油。因此曝露於照射光的_2⑻留下開口加，而保留非 照射區的光阻材料。—個將圖案開口观中的殘留光阻材料去除的步驟接著 進行，其通常係利用電漿乾蝕刻技術。 200842492 如第六圖’說明從光阻圖案轉移至金屬層13圖案之傳統過程。通常， 此過私係使用、種各向異性的電子束姓刻技術。經由電子束儀刻使圖案 2〇〇牙過整個金層13。本案上述健和在此—触巾齡其重要性。電 子束由圖案2〇0穿過金屬層U到達保護層U的上表面時。由於該保護層係以 對於鐳射束或電子束有抵抗力的㈣做成，該保護層U形成—緩衝之作 用，使基板11表面於蝕刻之過程中不會受到鐳射束或電子束之侵蝕，保持 基板11表面之完整性及平整度，俾使得該基板丨丨可再次回收使用。 重覆使用基板11時可選縣去或不除去上次使㈣保護層12，此乃取 決於保護層12在®案光罩製錢財受傷害的程度，由霞賴層雖係以 對於職束錢子束有抵抗力爾料做成，但過度之綱束缝子束仍有 可能造成保護層12受損。 如決定不除去上次使用的保護層12，其實施方案是將光罩浸入一具有 可與金屬層13材料產生蝕刻反應的脫膜液中，金屬層13被脫膜液蝕刻，因 此連帶使金屬層13上的抗反射層14、光阻層15等一併脫離基板11。以下為 保遵層12不脫膜之實施方案。需配製一種可與金屬層13材料產生蝕刻反應 的脫膜液，例如瑣酸銨鈽169g + 70%過氯酸26CC+純水調製成1000cc溶液。 將含有圖案的光罩移至一備有上述脫膜液的脫膜槽中，完全且充份靜置2〇 刀鐘後拉起移至清洗水槽，以南壓水沖洗基板，再將基板靜置於清洗水槽 10刀鐘，觀察基板是否透明，以確保金屬層13、抗反射層14以及光阻層15 全部脫離。 如第七圖，表示一種回收的基板11，該基板U上的金屬層13與脫膜液 200842492 反應後’该抗反射層14以及光阻層15全部自基板11處脫離。經過脫膜液處 理後之基板11，再次鍍製新金屬層13及抗反射層14 ,即可形成新的空白光 罩。 選擇除去保護層12，其實施方案是將光罩以上述方式脫膜，金屬層13 被脫膜液蝕刻，連帶使其上的抗反射層14、光阻層15—併脫離基板η，然 後將留有保護層12之光罩由清洗機以2%〜4%的HF(氫氟酸)蝕刻性溶液清 洗，直到除去圖案殘影，再重新鍍製新的保護層12及金屬層13及^^反射層 14。每一次都重新鍍製新的保護層12雖然成本較高，但可保證保護層12表 面之完整性及平整度。 如第八圖，表示一種回收的基板11，該基板u上的保護層12、金屬層 13、抗反射層η以及光阻層15全部脫離。 雖然本案是以一個最佳實施例做說明，但精於此技藝者能在不脫離本 案精神與範彆下做各種不同形式的改變。以上所舉實施例僅用以說明本案 而已，非用以限制本案之範圍。舉凡不違本案精神所從事的種種修改或變 化，倶屬本案申請專利範圍。 【圖式簡單說明】 第一圖為習知空白光罩的剖面簡圖。 第二圖為在習知空白光罩的光阻層上形成圖案的剖面簡圖。 第一0為將光阻層上的圖案形成在金屬層的剖面簡圖。 第四圖為本案空白光罩的剖面簡圖。 第五圖為在本案空自光罩的光崎上形細義剖面簡圖。 9 200842492 第六圖為將光阻層上的圖案形成在金屬層的剖面簡圖。 第七圖為本案回收基板的樣態之一。 第八圖為本案回收基板的樣態之二。 【主要元件符號說明】 ίο-空白光罩 11-基板 12-保護層 • 13-金屬層 14- 抗反射層 15- 光阻層 100-結構 ' 200-圖案 201-開口200842492 IX. Description of the invention: [Technical field to which the invention pertains] This case relates to the manufacturing technology of the ventilator, and more specifically, the technique of protecting the reticle substrate for repeated use, and This substrate recovery method. [Prior Art] In the manufacturing process of, for example, a structural semiconductor and a TFT element, a method for miniaturizing electronic components that is economical in time is to transfer a pattern on the substrate to the substrate by a pro-side mask. on. The patterned reticle is characterized by a misdirected beam or an electron beam after a surface-made photoresist layer called an empty reticle. As shown in Fig. 1, an empty mask is usually formed by plating a thin metal layer 52 (e.g., chromium, molybdenum, tungsten) on a glass or quartz substrate 51. Typical processes include: plating on a glass or quartz substrate - layer of chromium 52; secret riding on the mineral layer _ layer anti-reflective layer 53 to form a blank substrate (as shown in the first figure); A photoresist layer 54 is used; a desired pattern % is directly written on the photoresist layer 54 (as shown in the second figure); and a H-shaped pattern 59 is generated by a clock beam or an electron beam. ); and remove the residual photoresist layer. In the process of forming a pattern in the chrome layer, the surface of the quartz substrate is easily damaged by the laser beam or electron beam, which causes the surface of the substrate to be left behind and can no longer be used again. Shell is very expensive, and scrapping after one use will increase the manufacturing cost of the patterned mask to a large towel. It is therefore necessary to recycle the quartz substrate and then use it. In the conventional method, the soil plate is re-polished to remove the above layers and attempt to eliminate the pattern residual image on the substrate. However, the method of “recycling the substrate to recover the crucible is not only expected to cause a decrease in the surface precision of the substrate, but also causes the product to be questioned. After the polishing, the thickness of the substrate can not be recycled for many times, so that the number of times of recycling is limited, and the cost of precision grinding is extremely high, and the actual cost is not large. 200842492 [Summary of the Invention] The main purpose of the present invention is to provide a substrate for recycling. Reusable solution. This solution - in fact - is a measure to protect the substrate, in the process of blank mask manufacturing in the metal layer (such as the network, tungsten, tungsten) and the surface of the substrate to protect the material to avoid The substrate leaves a pattern afterimage in the process of deuterating the reticle. The present invention proposes a solution for recovering the substrate, which includes removing the protective material or removing the protective material. The implementation technology for achieving the above object is mainly in the production of blank light leather. During the process, a protective layer is plated between the gold-off layer and the surface of the substrate. The protective layer has a high transmittance. It can extend the performance stability of the substrate and increase the number of reuse of the substrate. The tilting layer of the present invention not only makes the substrate in the process of masking, but also leaves the residual image without being affected by the side, the mask is used more by the end customer. After that, the stripping method of the present invention can be performed to allow the substrate to be reused. The stripping method can be selected to remove or not remove the protective layer used last time. The protective layer is selected to be removed, and the embodiment is to immerse the mask in a protection and protection. The layer material produces a side-removing release film, the protective layer is on the liquid side, so that the metal layer, the anti-reflection layer, the photoresist layer, and the like on the protective layer are attached to and detached from the substrate. The embodiment is selected without removing the support layer. The immersion mask is immersed in a stripping liquid which can react with the metal layer material, and the metal layer is smothered. Therefore, the anti-reflection layer and the photoresist layer on the enamel layer are combined with the substrate, but on the substrate. [Embodiment] As shown in the fourth figure, a schematic cross-sectional view of a blank mask embodiment of the present invention, the blank mask (7) includes a substrate 11, a protective layer, and a metal layer 13 (such as chrome) from the bottom to the bottom. , 锢, tungsten); primary antibody The layer 200842492 may be plated on the surface of the metal layer 13, or may be plated between the metal layer 13 and the protective layer 12. In the drawing, the anti-reflection layer 14 is in the metal layer 13 and the photoresist layer 15. The protective layer 12 can be implemented by any material resistant to a laser beam or an electron beam. In a broad sense, it is a plating layer which can avoid the occurrence of marks on the substrate when the mask is patterned, and can be an anti-reflection layer or Highly penetrating layer. For example, in the manufacturing process of a deep ultraviolet laser direct writing laser mask, a magnesium fluoride (MgF〇 material can be used to realize the above protective layer. In the embodiment of the present invention, the refractive index of the protective layer 12 and the substrate The refractive index matching of 11 is expressed by the equation of t = A/4n, where t = thickness of the protective plating material; 乂-light wavelength, η = refractive index of the protective coating material, and the optimum refractive index of the protective coating is /~nsub. In the case of direct ultraviolet imaging of deep ultraviolet rays, the refractive index of the protective layer material is usually about 1.79 to 1.83. Therefore, the thickness of the protective layer is usually in the range of about 65 〇A to about 675 Å. And the refractive index of the protective ore layer is approximately in the range of 1.32 to 1.45. As shown in the fifth figure, a schematic diagram of the above-mentioned blank mask direct writing pattern in the present case will be described. The figure shows a blank reticle including the substrate 11, the protective layer 12, the metal layer 13, and the anti-reflection layer 14, and a structure 1 of a photoresist layer 15 on the surface of the blank reticle. Exposure to actinic radiation causes the photoresist layer 15 to pattern. After the photoresist layer 15 is patterned, the above-mentioned structure is set to a heat treatment in the special temperature range, and the chemical reaction is filled in the photoresist layer ls to transfer the pattern 2〇〇 to the entire thickness of the photoresist layer b. Inside, the pattern 2 is developed in a positive manner. After the pattern development, the above structure !00 is immersed in the developer liquid, and the dissolved photoresist material 15 is carried away from the base oil by the developer. Therefore, _2 (8) exposed to the illuminating light leaves an opening plus, while retaining the photoresist material in the non-irradiated area. A step of removing the residual photoresist material in the pattern opening view is followed by a plasma dry etching technique. 200842492 illustrates the conventional process of transferring from a photoresist pattern to a metal layer 13 pattern as shown in the sixth figure. Usually, this is a privately used, anisotropic electron beam surname technique. The pattern 2 is indented through the entire gold layer 13 via an electron beam apparatus. In this case, the above-mentioned health is here - the importance of the age of the towel. The electron beam passes through the metal layer U from the pattern 2〇0 to the upper surface of the protective layer U. Since the protective layer is made of (4) resistant to the laser beam or the electron beam, the protective layer U forms a buffering effect, so that the surface of the substrate 11 is not eroded by the laser beam or the electron beam during the etching process. The integrity and flatness of the surface of the substrate 11 are maintained so that the substrate can be recycled again. When the substrate 11 is repeatedly used, the optional county may or may not remove the last (four) protective layer 12, which depends on the extent to which the protective layer 12 is damaged by the reticle manufacturing money, and the Xia Lai layer is used for the service beam. The money bundle is made of resistance, but the excessive bundle of bundles may still cause damage to the protective layer 12. If it is decided not to remove the last used protective layer 12, the embodiment is to immerse the mask in a stripping liquid having an etching reaction with the material of the metal layer 13, and the metal layer 13 is etched by the stripping liquid, thereby causing the metal to be attached The anti-reflection layer 14, the photoresist layer 15, and the like on the layer 13 are separated from the substrate 11. The following is an implementation scheme for ensuring that the layer 12 is not released. It is necessary to prepare a stripping solution which can form an etching reaction with the material of the metal layer 13, for example, ammonium octoate 169g + 70% perchloric acid 26CC + pure water to prepare a 1000 cc solution. Move the mask containing the pattern to a stripping tank equipped with the above-mentioned stripping solution, completely and fully set to 2 knives, pull up and move to the washing tank, rinse the substrate with water in the south, and then rest the substrate. It was placed in a washing tank for 10 knives to observe whether the substrate was transparent to ensure that the metal layer 13, the anti-reflective layer 14, and the photoresist layer 15 were all separated. As shown in the seventh figure, a recovered substrate 11 is shown. After the metal layer 13 on the substrate U is reacted with the release liquid 200842492, the anti-reflection layer 14 and the photoresist layer 15 are all detached from the substrate 11. After the substrate 11 treated by the stripping solution is again plated with the new metal layer 13 and the anti-reflection layer 14, a new blank mask can be formed. The protective layer 12 is selectively removed. The embodiment is to remove the photomask in the above manner, and the metal layer 13 is etched by the stripping liquid, and the anti-reflective layer 14 and the photoresist layer 15 are attached thereto and separated from the substrate η, and then The mask with the protective layer 12 is cleaned by a cleaning machine with a 2% to 4% HF (hydrofluoric acid) etch solution until the pattern remains, and the new protective layer 12 and the metal layer 13 are re-plated. ^ Reflective layer 14. Each time the new protective layer 12 is re-plated, although the cost is high, the integrity and flatness of the surface of the protective layer 12 can be ensured. As shown in the eighth figure, a recovered substrate 11 is shown, on which the protective layer 12, the metal layer 13, the anti-reflection layer η, and the photoresist layer 15 are all detached. Although the present invention is described in terms of a preferred embodiment, those skilled in the art can make various changes in the form without departing from the spirit and scope of the present invention. The above embodiments are only used to illustrate the present case and are not intended to limit the scope of the present invention. Any modification or change that is not in violation of the spirit of the case is the scope of patent application in this case. [Simple description of the drawing] The first figure is a schematic sectional view of a conventional blank mask. The second figure is a schematic cross-sectional view of a pattern formed on a photoresist layer of a conventional blank mask. The first 0 is a schematic cross-sectional view in which a pattern on the photoresist layer is formed on the metal layer. The fourth picture is a schematic cross-sectional view of the blank mask of the present case. The fifth picture is a simplified cross-sectional view of the light-sense shape of the light mask in this case. 9 200842492 The sixth figure is a schematic cross-sectional view of the pattern on the photoresist layer formed on the metal layer. The seventh figure is one of the examples of the substrate recovery in this case. The eighth figure is the second form of the substrate for recycling this case. [Main component symbol description] ίο-blank reticle 11-substrate 12-protective layer • 13-metal layer 14-antireflection layer 15-resistive layer 100-structure '200-pattern 201-opening