200921269 九、發明說明： 【發明所屬之技術領域】 本發明係關於具備適於形成半節距4 5 n m以下高精度 微細圖案之遮光膜的空白光罩及光罩的製造方法。 【先前技術】 —般而言，在半導體裝置的製造步驟中，係使用光微 影法來進行微細圖案的形成。又，在該微細圖案的形成中， 通常使用任意片數被稱爲光罩的基板。該光罩係一般在透 光性的玻璃基板上’設置由金屬薄膜等所構成之遮光性微 細圖案者，即使在該光罩的製造中，仍使用光微影法。 在藉由光微影法之光罩的製造中，係使用在玻璃基板 等之透光性基板上具有遮光膜的空白光罩。使用該空白光 罩之光罩的製造’係針對在空白光罩上所形成的光阻膜， 具有實施所希望之圖案曝光的曝光步驟、依照所希望之圖 案曝光來顯像前述光阻膜而形成光阻圖案的顯像步驟 '沿 著光阻圖案來蝕刻前述遮光膜的蝕刻步驟、與剝離除去殘 存之光阻圖案的步驟來進行。在上述顯像步驟中，在針對 於空白光罩上所形成之光阻膜實施所希望的圖案曝光後供 給顯像液，溶解可溶於顯像液之光阻膜部位，而形成光阻 圖案。又，在上述蝕刻步驟中，以該光阻圖案爲光罩，藉 由例如乾式蝕刻，除去無光阻圖案形成之遮光膜的已曝光 部位，藉此在透光性基板上形成所希望的光罩圖案。如此 一來，完成光罩。 順道提及，近年來在半導體裝置的製造中，電路圖案 200921269 之微細化逐漸變得必要。因此，即使在光罩中亦要求以高 精度形成微細圖案。習知之遮光膜方面，大多使用鉻系化 合物。鉻系化合物係可藉由在主要成分之鉻中含有例如氧 或氮等元素，以調整遮光膜的膜應力或遮光膜的表面反射 率。當微細化在光罩所形成之遮光膜圖案（光罩圖案）時’ 取代習知濕式蝕刻而需要乾式蝕刻作爲空白光罩中之光阻 膜薄膜化與光罩製造時的蝕刻方法。 然而，光阻膜之薄膜化與乾式蝕刻加工則產生如下述 之技術問題。 如上述，習知遮光膜的材料方面，一般使用鉻系材料， 在鉻的乾式蝕刻加工中，在蝕刻氣體方面使用氯氣與氧氣 的混合氣體。在以光阻圖案作爲光罩而以乾式蝕刻來蝕刻 遮光膜時，由於光阻爲有機膜而其主成分爲碳，故對於其 爲乾式蝕刻環境之氧電漿而非常地弱。因此，在以乾式蝕 刻來圖案化遮光膜時，在該遮光膜上所形成之光阻圖案雖 必須殘留充分的膜厚，但在單純使光阻膜厚變厚且形成特 別微細之圖案的情況下，則產生縱橫尺寸比變大、圖案倒 塌等的問題。再者，在蝕刻氣體中使用氯氣與氧氣之混合 氣體的乾式蝕刻，由於指向性缺乏且等向性地進行蝕刻， 不利於以高精度形成4 5 n m半節距左右之微細圖案的情況。 因此’爲了盡量使光阻膜厚變薄、而且較具指向性之 異向性蝕刻爲可行，提案有使用矽化鉬系化合物（M〇Si)作 爲遮光膜材料，再者使該化合物中Mo的比例爲6〜20原子 %的技術（參照專利文獻丨）。 200921269 專利文獻1:特開2006-78807號公報 【發明說明】 發明所欲解決之問題 順道提及，爲了使用該等光罩以藉由曝光裝置（縮小投 影曝光裝置）而在半導體基板（矽晶圓）上進行圖案轉印’並 在半導體基板上以高精度形成例如4 5 nm半節距以下的微 細圖案，較佳爲在曝光裝置之光學系統中高開口數（高 NA)(NA > 1)之曝光方法，例如利用高NA透鏡或液浸。然 而，在利用該等高NA之曝光方法的情況下，受焦點深度 的影響而產生焦點位置的偏移，因該偏移而對於轉印圖案 精度或位置精度造成不良影響，結果爲產生所謂不能在半 導體基板上以高精密度形成例如4 5 nm半節距以下之微細 圖案的問題。 因此，在曝光裝置之光學系統中利用高N A之曝光方 法的情況下，要求即使因焦點深度之影響而使焦點位置偏 移，亦製作成爲可容許該偏移（的影響）的光罩。 因此，本發明之目的爲提供具備可應付在圖案轉印時 之曝光裝置中利用高NA之曝光方法情況之焦點深度的影 響，適合於在裝置上形成半節距45nm以下之高精度微細圖 案之遮光膜的空白光罩及光罩的製造方法。 解決課頴之丰跺 本發明者爲了解決上述課題而專心一志硏究的結果， 發現在以矽化鉬等之矽化金屬化合物來形成遮光膜的情況 下，藉由最適化例如鉬等金屬含有比例，即使受焦點深度 200921269 之影響而使焦點位置偏移，亦顯示可容許任何程度之該偏 移（的影響）的特性値變大，在有必要將矽化金屬化合物中 之金屬含有比例予以最適化的認識下繼續專心一志硏究的 結果，而達到本發明的完成。 即，爲了解決上述課題，本發明具有以下的構成。 (構成1) 一種空白光罩’其爲在透光性基板上具有遮光 膜的空白光罩，其特徵爲前述遮光膜包含金屬與矽（Si)，該 金屬含量相對於金屬與矽（Si)之合計爲小於6原子％。 (構成2)如記載於構成1之空白光罩，其特徵爲前述金 屬含量相對於金屬與矽（Si)之合計爲小於3原子％。 (構成3)如記載於構成1或2之空白光罩，其特徵爲前 述金屬爲鋁（M 0)。 (構成4)—種空白光罩，其爲在透光性基板上具有遮光 膜的空白光罩，其特徵爲前述遮光膜實質上係由矽（Si)所構 成。 (構成5)如記載於構成1至4中任一者之空白光罩，其 特徵爲前述遮光膜具有包含前述金屬與前述？^(Si)之遮光 層或實質上由前述矽（Si)所構成之遮光層、與形成於該遮光 層上之由含有氧與氮至少任一種之絡系化合物所構成的抗 反射層。 (構成6)如記載於構成5之空白光罩’其特徵爲在前述 遮光膜與前述透光性基板之間具有內面抗反射膜。 (構成7)—種光罩之製造方法’其特徵爲具有使用記載 於構成1至6中任一項之空白光罩’藉由乾式餓刻處理將 200921269 前述遮光膜予以圖案化的步驟。 如在構成1中，本發明之空白光罩係在透光性基板上 具有遮光膜的空白光罩，前述遮光膜包含金屬與矽（Si)，而 該金屬含量相對於金屬與矽（S i)之合計爲6原子％以下。 因此，由於在包含金屬與矽（Si)之遮光膜中所含的金屬 含量相對於金屬與矽（Si)之合計爲6原子％以下，故在使用 在透光性基板上形成有上述遮光膜之空白光罩所製作的光 罩中，在曝光裝置中利用高NA之曝光方法進行圖案轉印 的情況下，即使受焦點深度之影響而使焦點位置偏移，亦 可使顯示可容許任何程度該偏移（的影響）的特性値 (Exposure Latitude ：以下稱爲「.EL 値」。）變大。 因此，得到可應付在圖案轉印時之曝光裝置中利用高 NA曝光方法之情況的焦點深度影響、具備適合於在裝置上 形成例如半節距4 5 nm以下高精度微細圖案之遮光膜的空 白光罩及光罩。 又，如在構成2中，在構成1之前述金屬的含量相對 於金屬與矽（Si)之合計爲3原子％以下，由於可更合適發揮 本發明中之作用效果而特佳。 又，如在構成3中，較佳爲前述金屬爲鉬（Mo)。藉由 使矽化鉬化合物中之鉬含量成爲6原子％以下，較佳地得 到本發明中之作用效果，同時除了形成微細圖案之外’可 得到所希望之平滑性良好的遮光膜。 又，如在構成4中，本發明之空白光罩爲在透光性基 板上具有遮光膜的空白光罩，前述遮光膜實質上係由矽（Si) 200921269 所構成。藉由構成4之發明’亦可較佳地發揮本發明中之 作用效果。 又，如在構成5中’前述遮光膜可爲包含前述金屬與 前述矽（Si)之遮光層或實質上由前述矽（Si)所構成之遮光 層、與在該遮光層上所形成之含有氧與氮至少一種之鉻系 化合物所構成之抗反射層的積層構成，可減低對於曝光之 光線的表面反射率。又’由於抗反射層與遮光層具有乾式 蝕刻選擇性，故因已圖案化之抗反射層成爲下遮光層蝕刻 時的蝕刻光罩，即使減低遮光膜上之光阻膜厚，亦可精度 佳地形成微細圖案。 又，如在構成6中，在前述遮光膜與前述透光性基板 之間可具有內面抗反射膜。因此，由於具有該等內面抗反 射膜，因可防止在光罩內面側之曝光光線反射，特佳爲藉 由利用高NA曝光方法之曝光裝置來進行圖案轉印的情況。 又，如在構成7中，根據具有使用記載於構成〗至6 中任一項之空白光罩，藉由乾式蝕刻處理來蝕刻該空白光 罩遮光膜之步驟的光罩製造方法，得到上述之EL値大、因 此可應付在圖案轉印時之曝光裝置中利用高N A曝光方、法 情況之焦點深度的影響、具備適合於裝置上形成例如半節 距4 5 nm以下高精度微細圖案之遮光膜的光罩。 即，藉由本發明而得之光罩係可應付在曝光裝置中利 用高NA曝光方法情況之焦點深度的影響，而適合於進行 在裝置上以高精度進行半節距4 5 n m以下之微細圖案轉印。 發明效果 -10- 200921269 根據本發明，可提供具備適合於製造可應付在圖案轉 印時之曝光裝置中利用高NA曝光方法情況之焦點深度影 響之遮光膜的空白光罩。因此，藉由使用該等空白光罩來 製造光罩，可提供在圖案轉印時之曝光裝置中利用高NA 曝光方法，在進行半節距45 nm以下微細圖案轉印的情況下 得到良好轉印精度的光罩。 【實施方式】 實施發明之最佳形熊 / . 1 以下，參照圖式以詳述本發明之實施形態。 第1圖係顯示藉由本發明所得之空白光罩之一實施形 態的截面圖。 第1圖之空白光罩10係在透光性基板1上具有遮光膜 2之二進光罩用空白光罩的形態。 本實施形態之上述空白光罩1 0，係藉由蝕刻處理使在 前述遮光膜2上所形成之光圖案成爲光罩，適合對應於圖 案化前述遮光膜2之光罩製作方法之乾式飩刻處理用的空BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of manufacturing a blank mask and a photomask having a light-shielding film suitable for forming a high-precision fine pattern having a half pitch of 4 5 n m or less. [Prior Art] In general, in the manufacturing process of a semiconductor device, photolithography is used to form a fine pattern. Further, in the formation of the fine pattern, a substrate having a desired number of sheets called a photomask is usually used. In the reticle, a light-shielding fine pattern composed of a metal thin film or the like is generally provided on a light-transmitting glass substrate, and a photolithography method is used even in the production of the reticle. In the manufacture of a photomask by photolithography, a blank mask having a light-shielding film on a light-transmitting substrate such as a glass substrate is used. The manufacture of the photomask using the blank mask is directed to the photoresist film formed on the blank mask, having an exposure step for performing a desired pattern exposure, and exposing the photoresist film according to a desired pattern exposure. The developing step of forming the photoresist pattern is performed by a step of etching the light-shielding film along the photoresist pattern and a step of removing the remaining photoresist pattern by lift-off. In the above developing step, after the desired pattern exposure is applied to the photoresist film formed on the blank mask, the developing solution is supplied, and the photoresist film soluble in the developing solution is dissolved to form a photoresist pattern. . Further, in the etching step, the photoresist pattern is used as a mask, and the exposed portion of the light-shielding film formed without the photoresist pattern is removed by, for example, dry etching, thereby forming desired light on the light-transmitting substrate. Cover pattern. In this way, the mask is completed. Incidentally, in recent years, in the manufacture of semiconductor devices, the miniaturization of the circuit pattern 200921269 has become increasingly necessary. Therefore, it is required to form a fine pattern with high precision even in a photomask. In the conventional light-shielding film, a chromium-based compound is often used. The chromium-based compound can adjust the film stress of the light-shielding film or the surface reflectance of the light-shielding film by containing an element such as oxygen or nitrogen in the chromium of the main component. When the light-shielding film pattern (mask pattern) formed by the photomask is miniaturized, dry etching is required instead of the conventional wet etching as the etching method of the photoresist film thinning in the blank mask and the mask manufacturing. However, thin film formation and dry etching of a photoresist film cause technical problems as described below. As described above, in the material of the conventional light-shielding film, a chromium-based material is generally used, and in the dry etching process of chromium, a mixed gas of chlorine gas and oxygen gas is used for the etching gas. When the light-shielding film is etched by dry etching using the photoresist pattern as a mask, since the photoresist is an organic film and its main component is carbon, it is extremely weak for the oxygen plasma which is a dry etching environment. Therefore, when the light-shielding film is patterned by dry etching, the photoresist pattern formed on the light-shielding film must have a sufficient film thickness, but the thickness of the photoresist film is simply increased to form a particularly fine pattern. Next, there arises a problem that the aspect ratio becomes large, the pattern collapses, and the like. Further, dry etching using a mixed gas of chlorine gas and oxygen gas in the etching gas is not uniform and isotropically etched, which is disadvantageous in that a fine pattern of about 45 nm in half pitch is formed with high precision. Therefore, in order to make the thickness of the photoresist film as thin as possible and to make the anisotropic etching more directional, it is proposed to use a molybdenum molybdenum compound (M〇Si) as a light shielding film material, and further to make Mo in the compound. A technique in which the ratio is 6 to 20 atom% (refer to the patent document 丨). 200921269 Patent Document 1: JP-A-2006-78807 [Description of the Invention] Problems to be Solved by the Invention It is mentioned that in order to use the photomasks, the semiconductor substrate (the twin crystal) is used by the exposure device (reduced projection exposure device) The pattern transfer is performed on the circle] and a fine pattern of, for example, a half pitch of 45 nm or less is formed on the semiconductor substrate with high precision, preferably a high number of openings (high NA) in the optical system of the exposure apparatus (NA > 1 The exposure method, for example, using a high NA lens or liquid immersion. However, in the case of the exposure method using the contour NA, the shift of the focus position is caused by the influence of the depth of focus, and the offset causes an adverse effect on the accuracy of the transfer pattern or the positional accuracy, resulting in a so-called failure. A problem of forming a fine pattern of, for example, a half pitch of 45 nm or less at a high precision on a semiconductor substrate. Therefore, in the case where an exposure method of high N A is used in the optical system of the exposure apparatus, it is required to form a mask which can accommodate the offset even if the focus position is shifted due to the influence of the depth of focus. Accordingly, it is an object of the present invention to provide an effect of a depth of focus that can cope with an exposure method using a high NA in an exposure apparatus at the time of pattern transfer, and is suitable for forming a high-precision fine pattern having a half pitch of 45 nm or less on a device. A blank mask for a light-shielding film and a method of manufacturing the mask. In order to solve the above problems, the inventors of the present invention have found that when a light-shielding film is formed by a deuterated metal compound such as molybdenum molybdenum, it is found that the metal content ratio such as molybdenum is optimized. Even if the focus position is shifted by the influence of the depth of focus 200921269, it is shown that the characteristic 可 which can tolerate any degree of the offset is large, and it is necessary to optimize the metal content ratio in the deuterated metal compound. Under the understanding, continue to concentrate on the results of the study, and achieve the completion of the present invention. That is, in order to solve the above problems, the present invention has the following configuration. (Configuration 1) A blank mask which is a blank mask having a light-shielding film on a light-transmitting substrate, characterized in that the light-shielding film contains metal and bismuth (Si), and the metal content is relative to metal and bismuth (Si) The total is less than 6 atom%. (Configuration 2) The blank mask according to Configuration 1, characterized in that the metal content is less than 3 atom% with respect to the total of the metal and bismuth (Si). (Structure 3) The blank mask of the configuration 1 or 2 is characterized in that the metal is aluminum (M 0). (Configuration 4) A blank mask which is a blank mask having a light-shielding film on a light-transmitting substrate, characterized in that the light-shielding film is substantially made of yttrium (Si). (Configuration 5) The blank mask according to any one of Embodiments 1 to 4, wherein the light shielding film has the metal and the foregoing? A light-shielding layer of (Si) or a light-shielding layer consisting essentially of the above-mentioned bismuth (Si) and an anti-reflection layer comprising a complex compound containing at least one of oxygen and nitrogen formed on the light-shielding layer. (Configuration 6) The blank mask of the configuration 5 is characterized in that an inner surface anti-reflection film is provided between the light-shielding film and the light-transmitting substrate. (Structure 7) - A method of manufacturing a reticle, characterized in that the light-shielding film of 200921269 is patterned by dry hungry processing using the blank reticle described in any one of the structures 1 to 6. As in the configuration 1, the blank mask of the present invention is a blank mask having a light-shielding film on a light-transmitting substrate, the light-shielding film containing metal and germanium (Si), and the metal content is relative to the metal and germanium (S i The total amount is 6 atom% or less. Therefore, since the content of the metal contained in the light-shielding film containing metal and bismuth (Si) is 6 atom% or less with respect to the total of the metal and bismuth (Si), the above-mentioned light-shielding film is formed on the light-transmitting substrate. In the reticle produced by the blank reticle, when the pattern transfer is performed by the exposure method of high NA in the exposure apparatus, even if the focus position is shifted due to the influence of the depth of focus, the display can be allowed to any degree. The characteristic 値 (Exposure Latitude: hereinafter referred to as ".EL 値") of this offset is increased. Therefore, it is possible to obtain a blank which can cope with the influence of the depth of focus in the case where the high NA exposure method is used in the exposure apparatus at the time of pattern transfer, and has a light-shielding film suitable for forming a high-precision fine pattern of, for example, a half pitch of 45 nm or less on the apparatus. Photomask and reticle. In addition, in the structure 2, the content of the metal of the structure 1 is preferably 3 atom% or less based on the total of the metal and the yttrium (Si), and the effect of the present invention can be more suitably exhibited. Further, in the configuration 3, it is preferable that the metal is molybdenum (Mo). By setting the molybdenum content in the molybdenum molybdenum compound to 6 at% or less, it is preferable to obtain the effect of the present invention, and at the same time, in addition to the formation of the fine pattern, a desired light-shielding film having good smoothness can be obtained. Further, in the configuration 4, the blank mask of the present invention is a blank mask having a light-shielding film on a light-transmitting substrate, and the light-shielding film is substantially composed of 矽(Si) 200921269. The effect of the present invention can be preferably exerted by the invention of the constitution 4. Further, in the configuration 5, the light-shielding film may be a light-shielding layer including the metal and the ytterbium (Si) or a light-shielding layer substantially composed of the yttrium (Si), and a light-shielding layer formed on the light-shielding layer. A layered structure of an antireflection layer composed of at least one of a chromium-based compound of oxygen and nitrogen reduces the surface reflectance of the light to be exposed. Moreover, since the anti-reflection layer and the light-shielding layer have dry etching selectivity, since the patterned anti-reflection layer becomes an etching mask for etching the lower light-shielding layer, even if the photoresist film thickness on the light-shielding film is reduced, the precision can be improved. The ground forms a fine pattern. Further, in the configuration 6, the inner surface anti-reflection film may be provided between the light shielding film and the light-transmitting substrate. Therefore, since the inner surface anti-reflection film is provided, it is possible to prevent the reflection of the exposure light on the inner surface side of the photomask, and it is particularly preferable to carry out the pattern transfer by the exposure apparatus using the high NA exposure method. Further, in the configuration 7, the reticle manufacturing method having the step of etching the blank mask light-shielding film by dry etching using the blank mask described in any one of the structures 1-6 to 6 is obtained. Since the EL is large, it is possible to cope with the influence of the depth of focus in the case of the high-NA exposure method in the exposure apparatus at the time of pattern transfer, and it is suitable for forming a high-precision fine pattern of, for example, a half pitch of 45 nm or less. Film mask. That is, the photomask obtained by the present invention can cope with the influence of the depth of focus in the case of using the high NA exposure method in the exposure apparatus, and is suitable for performing the fine pattern of half pitch of 45 nm or less with high precision on the apparatus. Transfer. EFFECTS OF THE INVENTION -10-200921269 According to the present invention, it is possible to provide a blank mask having a light-shielding film suitable for producing a focus depth effect in a case where a high NA exposure method is used in an exposure apparatus at the time of pattern transfer. Therefore, by using the blank masks to manufacture the photomask, it is possible to provide a high-NA exposure method in the exposure apparatus at the time of pattern transfer, and to obtain a good transfer in the case of fine pattern transfer with a half pitch of 45 nm or less. Printed precision reticle. [Embodiment] The best shaped bear of the invention is implemented. Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. Fig. 1 is a cross-sectional view showing one embodiment of a blank mask obtained by the present invention. The blank mask 10 of Fig. 1 is a form in which a light-shielding substrate 1 has a blank mask for the mask of the light-shielding film 2. In the blank mask 10 of the present embodiment, the light pattern formed on the light shielding film 2 is formed into a mask by etching, and is suitable for dry etching of the mask manufacturing method for patterning the light shielding film 2. Empty space for processing
C 白光罩。 其中，透光性基板1方面，一般爲玻璃基板。由於玻 璃基板係平坦度及平滑度優異，在使用光罩來進行在半導 體基板上之圖案轉印的情況下，在不產生轉印圖案歪斜等 之下進行高精度的圖案轉印。 在上述空白光罩10上，前述遮光膜2係包含金屬與矽 (Si)，而該金屬含量相對於金屬與矽（Si)之合計爲6原子％ 以下。 200921269 因此’由於在包含金屬與矽（Si)之遮光膜中所含之金屬 含量相對於金屬與矽（Si)之合計爲6原子％以下，在使用在 透光性基板上形成有上述遮光膜之空白光罩所製作的光罩 上’在曝光裝置中利用尚NA曝光方法來進行圖案轉印的 情況下’即使受焦點深度之影響而使焦點位置偏移，仍可 增大顯不可容許任何程度該偏移（的影響）的特性値 (Exposure Latitude : EL値）。還有，隨著si量增加、或隨 者金屬量減少，光學上的値η或k變小。又，η或k變小 時，E L値變高。其中爲了 e L値達到本發明之效果’必要 之較佳的η與k値方面爲η$1且1(22.5。 因此’得到具備可應付在圖案轉印時之曝光裝置中利 用高NA曝光方法情況之焦點深度的影響、適合於在裝置 上形成例如半節距45iim以下高精度微細圖案之遮光膜的 空白光罩。藉由使用利用該等空白光罩所製造之光罩，在 圖案轉印時之曝光裝置中利用高N A曝光方法，進行半節 距45nm以下微細圖案之轉印的情況下，得到良好的轉印精 度。 在本發明中，爲了得到上述大的EL値，遮光膜中所含 之金屬含鼇相對於金屬與矽（Si)之合計宜爲6原子％以 下。又’在本發明中，特佳爲遮光膜中所含之金屬含量相 對於金屬與矽（Si)之合計爲3原子％以下。又，在本發明 中’較佳舄上述遮光膜實質上由矽（Si)所構成。 在本發明中，較佳爲前述金屬爲鉬（Mo)。由於砂化銷 化π物中之鉬含量小於6原子％ ’較佳地得到本發明中之 200921269 作用效果，同時由於以矽化鉬化合物形成遮光膜，因而在 形成微細圖案上可形成所希望之平滑性良好的遮光膜。 又’上述遮光膜2係鋁等金屬與矽含量在深度方向爲 段階性或連續性差異的組成傾斜膜均可。 又’上述遮光膜2係可爲具有包含以前述金屬與矽（Si) 爲主之構成成分的遮光層、包含以砂（Si)爲主之構成成分的 遮光層、與在該遮光層上所形成之由含氧與氮中至少一種 之鉻系化合物所構成之抗反射層的積層構成。總之，遮光 膜2亦可在表層部份（上層部份）包含抗反射層。在該情況 下，抗反射層方面，較佳地舉例有CrO、CrCO、CrN、CrNO、 CrC ON等材質。藉由設置抗反射層，由於可抑制曝光波長 中之反射率於例如2 0 %以下、較佳爲1 5 %以下，故在轉印 光罩圖案至被轉印體上時，抑制在投影曝光面之間的多重 反射、可抑制成像特性的降低。再者，雖然相對於在空白 光罩或光罩之缺陷檢査中所用之波長（例如 2 5 7nm、 364nm、488nm等）的反射率爲例如30%以下，但希望以高 精度檢測出缺陷。 又，藉由設置鉻系之抗反射層，由於抗反射層與遮光 層具有乾式飩刻選擇性，在光罩製造時，首先以遮光膜上 之光阻圖案爲光罩來圖案化抗反射層，因已圖案化之抗反 射層成爲下遮光層之圖案化時的鈾刻光罩’可減低遮光膜 上之光阻膜厚，可精度佳地形成微細圖案。 還有，在鉻系抗反射層的情況下，由於鉻中含有氧或 氮，可提升乾式蝕刻速度，又可藉由氮含量來調整膜應力。 200921269 抗反射層之膜應力係在無損及空白光罩之平坦性之下，希 望以兼具與包含金屬與矽（s】）之遮光層的膜應力來適宜調 整。 上述遮光膜2的形成方法雖無需要特別限制，但特佳 爲舉出噴鍍成膜法。藉由噴鍍成膜法時，由於可均一地形 成膜厚一定的薄膜’而適合於本發明。在透光性基板1上， 在藉由噴鍍成膜法使上述遮光膜2中之遮光層成膜的情況 下，使用鉬（Mo)與矽（Si)之混合靶子作爲噴鍍靶子，導入 於反應室內的噴鑛氣體係使用氬氣或氦氣等惰性氣體。 又’在使鉻系之抗反射層成膜的情況下，使用鉻（C r)靶子 作爲噴鍍靶子’導入反應室內之噴鍍氣體係使用在氬氣或 氦氣等惰性氣體中混合氧、氮等氣體者。使用混合氬氣等 惰性氣體與氧氣等而成的噴鍍氣體時，可形成在鉻中含氧 的抗反射層，使用混合氬氣等惰性氣體與氮氣而成之噴鍍 氣體時’可形成在鉻中含氮的抗反射層，又使用在氬氣等 惰性氣體中混合氮氣等之噴鍍氣體時，可形成在鉻中含氮 與氧的抗反射層。 上述遮光膜2之膜厚係希望設定爲相對於曝光光線爲 光學濃度2.5以上。具體而言，上述遮光膜2的膜厚較佳 爲90nm以下。該理由係爲了應付近年之達到次微米等級圖 案尺寸之圖案微細化，膜厚超過9 0 n m時，則因乾式蝕刻時 圖案之微型加載現象，而認爲有微細圖案之形成變困難的 情況。藉由某程度使膜厚變薄，可謀求圖案之縱橫尺寸比 (相對於圖案寬度之圖案深度比）的減低，並可減低因總體 -14- 200921269 加載現象及微型加載現象所導致線寬誤差。 又，在本發明中，可在前述遮光膜2與前述透光性基 板1之間形成內面抗反射膜。因此，藉由形成內面抗反射 膜，由於可有效防止在光罩內面側之曝光光線反射，特佳 爲藉由利用高NA曝光方法之曝光裝置來進行圖案轉印的 情況。該等內面抗反射膜的材料方面，雖然在本發明中並 無特別限制，但考慮例如與遮光膜2之蝕刻選擇性等時， 較佳地舉例有Μ 〇 S i Ο N等。 又，本發明之空白光罩方面，如在後述之第2(a)圖中， 即使是在上述遮光膜2上形成光阻膜3的形態亦無妨。光 阻膜3之膜厚係爲了使遮光膜的圖案精度（c 〇精度）良好， 較佳爲盡可能的薄。在如本實施形態之所謂二進光罩用空 白光罩的情況下，具體而言’光阻膜3之膜厚較佳爲i 5 〇 n m 以下。更佳則希望爲1 0 0 n m以下。又，爲了得到高解析度， 光阻膜3之材料較佳爲光阻感度高之化學擴大型光阻。 其次’說明使用示於第1圖之空白光罩1〇的光罩製造 方法。 使用該空白光罩10之光罩製造方法具有使用乾式蝕 刻來圖案化空白光罩10之遮光膜2的步驟，具體而言，具 有針對在空白光罩10上所形成之光阻膜實施所希望之圖 案描繪的步驟、依照所希望之圖案描繪來顯像前述光阻膜 以形成光阻圖案的步驟、依照光阻圖案來乾式蝕刻前述遮 光膜的步驟、與剝離除去所殘存之光阻圖案的步驟。 第2圖係依序顯示使用空白光罩1〇之光罩製造步驟的 200921269 截面圖。 第2(a)圖係顯示在第1圖空白光罩10之遮光膜2上形 成光阻膜3的狀態。還有，光阻材料方面，使用正型光阻 材料 '或負型光阻材料均司·。 其次’第2(b)圖係顯示針對在空白光罩1〇上所形成之 光阻膜3 ’實施所希望之曝光（圖案描繪）的步驟。圖案描繪 係使用電子線束描繪裝置等來進行。上述光阻材料係使用 具有對於電子線束或雷射的感光性者。 其次’第2(c)圖係顯示依照所希望之圖案描繪來顯像 光阻膜3以形成光阻圖案3a的步驟。在該步驟中，在針對 在空白光罩10上所形成之光阻膜3實施所希望之圖案描繪 後供給顯像液’溶解可溶於顯像液之光阻膜部位，而形成 光阻圖案3 a。 其次’第2 (d)圖係顯示沿著上述光阻圖案3 3來蝕刻遮 光膜2的步驟。由於本發明之空白光罩適合於乾式蝕刻， 故較佳爲蝕刻係使用乾式蝕刻。在該蝕刻步驟中，以上述 光阻圖案3 a爲光罩，藉由乾式蝕刻，除去未形成光阻圖案 3 a之遮光膜2已露出的部位，藉此在透光性基板1上形成 所希望的遮光膜圖案2 a(光罩圖案）。 在該乾式蝕刻中，針對包含金屬與矽（Si)之遮光層，可 使用氟系氣體作爲蝕刻氣體，針對包含鉻系化合物之抗反 射層’則可使用由氯系氣體、或由氯系氣體與氧氣之混合 氣體所構成的乾式蝕刻氣體。 第2 ( e)圖係顯示藉由剝離除去殘存之光阻圖案3 a所得 200921269 的光罩2 0。 藉由使用該等本發明之空白光罩來製作光罩，可在光 罩上精度佳地形成例如在裝置上之相當4 5 nm半節距以下 的微細圖案。 又’在EL値大、在曝光裝置中利用高NA曝光方法的 情況下’即使受焦點深度之影響而使焦點位置偏移，亦在 可容許該不均一（的影響）之下得到光罩。即，藉由本發明 所得之光罩，較佳爲可應付在曝光裝置中利用高N A曝光 方法情況之焦點深度的影響、以高精度進行圖案轉印半節 距4 5 nm以下微細圖案至被轉印體上。 實施例 以下’藉由實施例來更具體說明本發明之實施形態。 並且’亦說明相對於實施例的比較例。 (實施例1 ：> #實施例之空白光罩係在透光性基板上形成遮光膜與 抗反射膜者。 該空白光罩係可由如以下之方法來製造。 胃密硏磨主表面及終端面，在由基板主表面之形狀已 ® I fP成凸狀之合成石英玻璃所構成的透光性基板（大小 爲1 52mmx丨52mm)上，使用葉片式噴鍍裝置，在噴鍍靶子 上使用鉬（Μ 〇 )與矽（S i)的混合靶子（Μ 〇 : S i = 5 : 9 5原子 %)，在氬氣（Ar)氛圍氣體中，藉由噴鍍（DC噴鍍），形成膜 厚35 nrn之以鉬與矽爲主要構成要素的遮光層。之後，以 5 0 0 °C進行加熱處理3小時。 200921269 其次，藉由在噴鍍靶子上使用鉻靶子，在氬氣、氮與 氧之混合氣體（Ar: 30體積％、N2: 35體積％、〇2: 35體 積％)氛圍氣體中進行反應性噴鍍’形成膜厚20nm之在鉻 中包含氧與氮的抗反射層。如此一來’製造在透光性基板 上形成由總膜厚爲55nm之遮光層及抗反射層所構成之遮 光膜的空白光罩。 又，該空白光罩中之遮光膜係在遮光層與其上之抗反 射層的積層構造中，在例如曝光波長I93nm中之光學濃度 f · 爲3.0以上。又，在曝光波長193nm中之反射率係可抑制 低至16%。再者，針對其爲光罩缺陷檢査波長之2 5 7nm則 爲18%，即使在進行檢査方面亦無成問題的反射率。 其次，針對上述空白光罩，爲了在遮光膜上所形成之 光阻膜的附著力提升，考慮光阻種類而進行在1 60 °c的烘 烤處理。其次，在上述空白光罩上，形成膜厚15 Onm之其 爲化學擴大型光阻的電子線束光阻膜（富士軟片電子材料 公司製CAR-FEP171)。光阻膜之形成係使用旋轉器（旋轉塗 布裝置）來旋轉塗布。還有，塗布上述光阻膜後，進行在 1 3 0°C的預烘烤處理。 其次針對在空白光罩上所形成之光阻膜，在使用電子 線束描繪裝置，進行相當於裝置中之45nm半節距的圖案描 繪後，以既定之顯像液顯像而形成光阻圖案。 其次，沿著上述光阻圖案，首先進行抗反射層之乾式 蝕刻以形成抗反射層圖案。使用Cl2與02之混合氣體（Cl2: 〇2 = 4 : 1)作爲此時之乾式蝕刻氣體。 200921269 其次’以上述抗反射層圖案及光阻圖案爲光罩，進行 遮光層之乾式蝕刻而形成遮光膜圖案。使用SF6與He之混 合氣體作爲此時的乾式蝕刻氣體。 其次’剝離殘存之光阻圖案而得到光罩。所形成之遮 光膜圖案的c D損失（c D誤差）（相對於設計線寬之實測線寬 的偏移）爲小至20nm’光罩上之遮光膜圖案的圖案精度亦 如設計般的良好。 藉由計算軟體（例如EM-套裝第五版），例如光學條件 ( 爲λ = 1 9 3 n m、N A = 1 _ 3，求得如以上所得之本實施例的光罩 EL値。 藉由以上方法，求得本實施例之光罩EL値的結果，與 後述比較例之光罩EL値比較則爲大的値。附帶說明，在 nSl、k^2.5的範圍內。因此，藉由使用高NA曝光方法 的曝光裝置’在使用該光罩以在半導體基板上進行圖案轉 印的情況下，即使受焦點深度之影響而使焦點位置偏移， 亦可充分容許該偏移（的影響），該結果爲可以如設計般地 ι 高精度，在半導體基板上形成相當於45nm半節距的微細圖 案。 (實施例2) 在由與實施例1相同之合成石英玻璃所構成之透光性 基板上，使用葉片式噴鍍裝置，在噴鍍靶子上使用鉬（Mo) 與矽（Si)之混合靶子（Mo: Si = 3: 97原子％)，在氬氣（Ar) 氛圍氣體中，藉由噴鍍（DC噴鍍），形成膜厚33nm以鉬與 矽爲主要構成要素的遮光層。之後，以5 〇 〇。<3進行加熱處 200921269 理3小時。 其次，在上述遮光層上，與實施例1同樣地形成抗反 射層，製作空白光罩。 本實施例之空白光罩爲在曝光波長193 nm之光學濃度 爲3 · 0以上。又，可抑制在該曝光波長1 9 3 n m之反射率低 至 1 9 %。 使用如此所得之空白光罩，與實施例1同樣地製作光 罩。 即使在本實施例中，所形成之遮光膜圖案的c D損失 (CD誤差）（相對於設計線寬之實測線寬的偏移）亦小至 2 0 n m，光罩上之遮光膜圖案的圖案精度亦如設計般地良好。 與實施例1同樣地求得本實施例光罩之E L値的結果爲 高的値。該値與後述之比較例的光罩EL値比較則爲大的 値。附帶說明，在n S I、k 2 2.5的範圍內。因此，藉由使 用高N A曝光方法的曝光裝置，在使用本實施例之光罩以 在半導體基板上進行圖案轉印的情況下，即使受到焦點深 度之影響而使焦點位置偏移，亦可充分容許該偏移（的影 響）’該結果爲可以如設計般地高精度’在半導體基板上形 成相當於4 5 n m半節距的微細圖案。 (實施例3 ) 在由與實施例1相同之合成石英玻璃所構成之透光性 基板上，使用葉片式噴鍍裝置’在噴鍍靶子上使用鉬（Mo) 與矽（Si)之混合靶子（Mo: Si = 5: 95原子％)，在氬氣（Ar) 與氧氣和氮氣之混合氣體（Ar: 體積％、〇2: 10體積％、 -20- 200921269 N2 : 80體積％ )的氛圍氣體中，藉由噴鍍（DC噴鍍）’形成 膜厚10nm之在鉬與矽中含氧與氮的內面抗反射膜。 其次，在上述內面抗反射膜上，與實施例1同樣地形 成遮光層及抗反射層，以製作空白光罩。但是，本實施例 之遮光層膜厚爲35nm、抗反射層膜厚爲20nm。 本實施例之空白光罩係在曝光波長193 nm中之光學濃 度爲3.0以上。又，在該曝光波長193nm中之遮光膜表面（抗 反射層表面）的反射率係可抑制低至1 6 %。然後，較佳爲亦 可抑制空白光罩之內面側的反射率低至2 5 %，特別是進行 藉由使用高NA曝光方法之曝光裝置的圖案轉印的情況。 使用如此所得之空白光罩，與實施例1同樣地製作光 罩。即，針對在空白光罩上所形成之光阻膜，使用電子線 束描繪裝置來進行相當於45nm半節距的圖案描繪後，顯像 而形成光阻圖案。其次，與實施例1同樣地，沿著上述光 阻圖案，首先進行抗反射層之乾式蝕刻以形成抗反射層的 圖案。 其次，以上述抗反射層圖案及光阻圖案爲光覃，進行 遮光層及內面抗反射膜的乾式蝕刻而形成遮光膜及內面抗 反射膜的圖案。 其次，剝離殘存的光阻圖案，而得到光罩。即使在本 實施例中，所形成之遮光膜圖案的C D損失（C D誤差）（相對 於設計線寬之實測線寬的不均一）亦小至20nm，光罩上之 遮光膜圖案的圖案精度亦如設計般地良好。 與實施例1同樣地求得本實施例光罩之E L値的結果爲 -21- 200921269 高的値。該値與後述之比較例的光罩EL値比較則爲大的 値。附帶說明，在n S 1、k 2 2.5的範圍內。因此，藉由使 用高NA曝光方法的曝光裝置，在使用本實施例之光罩以 在半導體基板上進行圖案轉印的情況下，即使受到焦點深 度之影響而使焦點位置偏移，亦可充分容許該偏移（的影 響），該結果爲可以如設計般地高精度在半導體基板上形成 相當於45 nm半節距的微細圖案。 (比較例1) 在由與實施例1相同之合成石英玻璃所構成之透光性 基板上，使用葉片式噴鍍裝置，在噴鍍靶子上使用鉬（Mo) 與矽（Si)之混合靶子（Mo: Si=7: 93原子％)，在氬氣（Ar) 的氛圍氣體中，藉由噴鍍（DC噴鑛），形成膜厚42nm之以 鉬與矽爲主之構成要素的遮光層。 其次，在上述遮光層上，與實施例1同樣地形成抗反 射層’以製作空白光罩。但是，本比較例之抗反射層膜厚 爲 2 0 n m 〇 本比較例之空白光罩係在曝光波長193nm中之光學濃 度爲3.0以上。又，可抑制該曝光波長I93nm中之反射率 低至1 4 %。 使用如此所得之空白光罩，與實施例1同樣地製作光 罩。 與實施例1同樣地求得遮光膜中Μ 〇含量爲7原子％ 之本比較例的光罩之EL値的結果爲低値。由於該値與遮光 膜中Mo含量爲6原子％以下之上述各實施例的光罩EL値 -22 - 200921269 比較爲小，故使用該光罩，藉由使用高ΝΑ曝光方法之曝 光裝置來進行在半導體基板上的圖案轉印時’不能容許光 學系統之焦點深度的影響’難以如設計般地高精度在半導 體基板上形成相當於4 5 n m半節距的微細圖案。 (比較例2) 在由與實施例1相同之合成石英玻璃所構成之透光性 基板上，使用葉片式噴鍍裝置，在噴鍍靶子上使用鉬（Mo) 與矽（Si)之混合靶子（Mo: Si=7: 93原子％)，在氬氣（Ar) 與氮和氧之混合氣體（Ar: 1〇體積％、N2: 80體積％、02: 1〇體積％)的氛圍氣體中，藉由噴鍍（DC噴鍍），形成膜厚 1 〇nm之在鉬與矽中含氧與氮的內面抗反射膜。 其次，在上述內面抗反射膜上，同樣地使用葉片式噴 鍍裝置，在噴鍍靶子上使用鉬（Mo)與矽（Si)之混合靶子 (Mo: Si=7: 93原子％)，在氬氣（Ar)的氛圍氣體中，藉由 噴鍍（DC噴鍍），形成膜厚42ηηι之以鉬與矽爲主要構成要 素的遮光層。 其次，在上述遮光層上，與實施例1同樣地形成抗反 射層，以製作空白光罩。但是，本比較例之抗反射層膜厚 爲 2 0 n m。 本比較例之空白光罩係在曝光波長193 nm中之光學濃 度爲3.0以上。又，可抑制該曝光波長1 9 3 nm中之反射率 低至1 4 %。然後，亦可抑制空白光罩之內面側的反射率低 至 22%。 使用如此所得之空白光罩，與實施例3同樣地製作光 -23- 200921269 罩。 與實施例1同樣地求得本比較例的光罩之E L値的，結$ 爲低値。由於該値與遮光膜中Mo含量爲6原子％&τ之 上述各實施例的光罩E L値比較爲小，故使用該光罩，_ _ 使用高ΝΑ曝光方法之曝光裝置來進行在半導體基丨反±白勺 圖案轉印時，不能容許光學系統之焦點深度的影響，_ & 如設計般地高精度在半導體基板上形成相當於4 5 nm _ |t5 距的微細圖案。 【圖式簡單說明】 第1圖係顯示本發明之空白光罩之一實施形態的m胃 圖。 第2圖系顯示使用空白光罩之光罩製造步驟的胃胃 圖。 【主要元件符號說明】 1 透 光 性 基 板 2 遮 光 膜 3 光 阻 膜 2 a 遮 光 膜 圖 案 3a 光 阻 圖 案 10 空 白 光 罩 20 光 罩C white hood. Among them, the translucent substrate 1 is generally a glass substrate. Since the glass substrate is excellent in flatness and smoothness, when pattern transfer on a semiconductor substrate is performed using a photomask, high-precision pattern transfer is performed without causing skew of the transfer pattern or the like. In the blank mask 10, the light-shielding film 2 contains a metal and bismuth (Si), and the metal content is 6 atom% or less based on the total of the metal and bismuth (Si). 200921269 Therefore, the above-mentioned light-shielding film is formed on the light-transmitting substrate because the total content of the metal contained in the light-shielding film containing the metal and yttrium (Si) is 6 atom% or less based on the total of the metal and the yttrium (Si). In the case where the mask is made by the blank mask, in the case where the image is transferred by the NA exposure method in the exposure apparatus, even if the focus position is shifted due to the influence of the depth of focus, it can be increased or not. The degree of this offset (the effect of the impact) (Exposure Latitude: EL値). Also, as the amount of si increases, or as the amount of metal decreases, the optical 値η or k becomes smaller. Further, when η or k becomes small, E L 値 becomes high. In order to achieve the effect of the present invention in order to achieve the effect of the present invention, the preferred η and k値 are η$1 and 1 (22.5. Therefore, it is possible to obtain a high-NA exposure method which can cope with the exposure apparatus at the time of pattern transfer. The influence of the depth of focus, a blank mask suitable for forming a light-shielding film of, for example, a high-precision fine pattern having a half pitch of 45 μm or less on the device. By using a photomask manufactured using the blank masks, at the time of pattern transfer In the exposure apparatus, when the transfer of the fine pattern having a half pitch of 45 nm or less is performed by the high NA exposure method, good transfer accuracy is obtained. In the present invention, in order to obtain the above large EL 値, the light shielding film is included. The metal-containing cerium is preferably 6 atomic % or less based on the total of the metal and cerium (Si). Further, in the present invention, it is particularly preferable that the total content of the metal contained in the light-shielding film is relative to the total amount of metal and cerium (Si). Further, in the present invention, it is preferable that the light-shielding film is substantially composed of yttrium (Si). In the present invention, it is preferable that the metal is molybdenum (Mo). Molybdenum content less than 6 The sub-%' preferably obtains the effect of the 200921269 in the present invention, and at the same time, since the light-shielding film is formed by the molybdenum molybdenum compound, a desired light-shielding film having good smoothness can be formed on the fine pattern. The metal such as aluminum and the composition of the ruthenium may have a stepwise or continuous difference in the depth direction. The above-mentioned light shielding film 2 may have a light shielding layer containing a constituent mainly composed of the above metal and bismuth (Si). And a light-shielding layer containing a constituent component mainly composed of sand (Si) and an anti-reflection layer composed of a chromium-based compound containing at least one of oxygen and nitrogen formed on the light-shielding layer. The film 2 may also include an antireflection layer in the surface layer portion (upper layer portion). In this case, as the antireflection layer, materials such as CrO, CrCO, CrN, CrNO, CrC ON, etc. are preferably exemplified. In the reflective layer, since the reflectance in the exposure wavelength can be suppressed to, for example, 20% or less, preferably 15% or less, when the reticle pattern is transferred onto the transfer target, the projection between the projection exposure surfaces is suppressed. Multiple The radiation can suppress the deterioration of the imaging characteristics. Further, although the reflectance with respect to the wavelength (for example, 257 nm, 364 nm, 488 nm, etc.) used for the defect inspection of the blank mask or the photomask is, for example, 30% or less, It is desirable to detect defects with high precision. Moreover, by providing a chromium-based anti-reflection layer, since the anti-reflection layer and the light-shielding layer have dry etching selectivity, in the manufacture of the mask, first, the photoresist pattern on the light-shielding film is used. The mask is used to pattern the anti-reflection layer, and the uranium engraved mask when the patterned anti-reflection layer is patterned by the lower light-shielding layer can reduce the thickness of the photoresist film on the light-shielding film, and can form a fine pattern with high precision. Further, in the case of the chromium-based antireflection layer, since chromium contains oxygen or nitrogen, the dry etching rate can be increased, and the film stress can be adjusted by the nitrogen content. 200921269 The film stress of the anti-reflective layer is under the flatness of the non-destructive and blank mask, and it is desirable to adjust it with the film stress of the light-shielding layer containing the metal and bismuth (s). The method for forming the light-shielding film 2 is not particularly limited, but a thermal spray film formation method is particularly preferred. In the case of the thermal spray film formation method, a film having a constant film thickness can be uniformly formed, which is suitable for the present invention. In the case where the light-shielding layer in the light-shielding film 2 is formed by a thermal spray coating method on the light-transmitting substrate 1, a mixed target of molybdenum (Mo) and bismuth (Si) is used as a sputtering target. An inert gas such as argon gas or helium gas is used in the sprayed ore gas system in the reaction chamber. Further, when a chromium-based antireflection layer is formed, a sputtering gas system introduced into a reaction chamber using a chromium (Cr) target as a sputtering target is mixed with oxygen in an inert gas such as argon gas or helium gas. Nitrogen and other gases. When a sputtering gas obtained by mixing an inert gas such as argon gas and oxygen gas is used, an anti-reflection layer containing oxygen in chromium can be formed, and when a gas is sprayed using an inert gas such as argon gas and nitrogen gas, it can be formed. In the anti-reflection layer containing nitrogen in chromium, when an inert gas such as argon gas is mixed with a sputtering gas such as nitrogen gas, an anti-reflection layer containing nitrogen and oxygen in chromium can be formed. The film thickness of the light-shielding film 2 is desirably set to be an optical density of 2.5 or more with respect to the exposure light. Specifically, the film thickness of the light shielding film 2 is preferably 90 nm or less. The reason for this is to cope with the pattern miniaturization of the sub-micron pattern size in recent years. When the film thickness exceeds 90 nm, it is considered that the formation of a fine pattern is difficult due to the micro-loading phenomenon of the pattern during dry etching. By reducing the film thickness to some extent, the aspect ratio of the pattern (the pattern depth ratio with respect to the pattern width) can be reduced, and the line width error caused by the loading phenomenon and the micro-loading phenomenon of the overall-14-200921269 can be reduced. . Further, in the present invention, an inner surface anti-reflection film can be formed between the light-shielding film 2 and the light-transmitting substrate 1. Therefore, by forming the inner anti-reflection film, it is possible to effectively prevent the reflection of the exposure light on the inner surface side of the photomask, and it is particularly preferable to carry out the pattern transfer by the exposure apparatus using the high NA exposure method. Although the material of the inner surface anti-reflection film is not particularly limited in the present invention, for example, when etching selectivity with the light-shielding film 2 or the like is considered, Μ 〇 S i Ο N or the like is preferably exemplified. Further, in the blank mask of the present invention, as shown in the second (a) drawing to be described later, the photoresist film 3 may be formed on the light-shielding film 2. The film thickness of the photoresist film 3 is preferably as thin as possible in order to improve the pattern accuracy (c 〇 precision) of the light-shielding film. In the case of the so-called dichroic mask for the reticle according to the present embodiment, specifically, the film thickness of the photoresist film 3 is preferably i 5 〇 n m or less. More preferably, it is desirably less than 1 0 0 n m. Further, in order to obtain high resolution, the material of the photoresist film 3 is preferably a chemically amplified photoresist having high photoresist sensitivity. Next, a method of manufacturing a mask using the blank mask 1 shown in Fig. 1 will be described. The mask manufacturing method using the blank mask 10 has a step of patterning the light shielding film 2 of the blank mask 10 using dry etching, specifically, having a desired effect on the photoresist film formed on the blank mask 10. a step of pattern drawing, a step of developing the photoresist film to form a photoresist pattern according to a desired pattern, a step of dry etching the light shielding film according to the photoresist pattern, and removing the remaining photoresist pattern by lift-off step. Figure 2 is a cross-sectional view showing the 200921269 cross-section of the reticle manufacturing step using a blank mask. Fig. 2(a) shows a state in which the photoresist film 3 is formed on the light shielding film 2 of the blank mask 10 of Fig. 1. Also, in terms of photoresist materials, positive-type photoresist materials or negative-type photoresist materials are used. Next, the second (b) figure shows the step of performing the desired exposure (pattern drawing) on the photoresist film 3' formed on the blank mask 1'. The pattern drawing is performed using an electron beam drawing device or the like. The above-mentioned photoresist material is used to have sensitivity to electron beam or laser. Next, the second (c) drawing shows the step of developing the photoresist film 3 to form the photoresist pattern 3a in accordance with a desired pattern. In this step, after the desired pattern drawing is performed on the photoresist film 3 formed on the blank mask 10, the developing solution is supplied to dissolve the photoresist film portion soluble in the developing liquid to form a photoresist pattern. 3 a. Next, the second (d) figure shows the step of etching the light-shielding film 2 along the above-described photoresist pattern 33. Since the blank mask of the present invention is suitable for dry etching, it is preferred that the etching system use dry etching. In the etching step, the photoresist pattern 3 a is used as a mask, and the exposed portion of the light-shielding film 2 in which the photoresist pattern 3 a is not formed is removed by dry etching, whereby the light-transmissive substrate 1 is formed. A desired light shielding film pattern 2 a (mask pattern). In the dry etching, a fluorine-based gas can be used as the etching gas for the light-shielding layer containing metal and bismuth (Si), and a chlorine-based gas or a chlorine-based gas can be used for the anti-reflection layer containing the chromium-based compound. A dry etching gas composed of a mixed gas with oxygen. The second (e) figure shows the mask 20 of 200921269 obtained by peeling off the remaining photoresist pattern 3a. By fabricating the reticle using the blank reticle of the present invention, a fine pattern of, for example, a half pitch of 45 nm or less on the device can be accurately formed on the reticle. Further, in the case where the EL is large and the high NA exposure method is used in the exposure apparatus, the focus position is shifted even under the influence of the depth of focus, and the mask can be obtained under the influence of the unevenness. That is, with the reticle obtained by the present invention, it is preferable to cope with the influence of the depth of focus in the case of using the high NA exposure method in the exposure apparatus, and to perform pattern transfer with a high precision of a fine pattern of 45 nm or less to be rotated. On the print. EXAMPLES Hereinafter, embodiments of the present invention will be described more specifically by way of examples. And 'comparative examples with respect to the examples are also explained. (Embodiment 1: >#The blank mask of the embodiment is a light-shielding film and an anti-reflection film formed on a light-transmitting substrate. The blank mask can be manufactured by the following method. The main surface of the stomach is honed and The terminal surface is a light-transmissive substrate (having a size of 1 52 mm x 丨 52 mm) composed of a synthetic quartz glass having a shape of a main surface of the substrate, and a vane type sputtering apparatus is used on the sputtering target. Using a mixed target of molybdenum (Μ 〇) and 矽 (S i ) (Μ 〇: S i = 5 : 9.5 atomic %), by sputtering (DC sputtering) in an argon (Ar) atmosphere, A light-shielding layer having a thickness of 35 nrn and containing molybdenum and niobium as main constituent elements was formed. Thereafter, heat treatment was performed at 500 ° C for 3 hours. 200921269 Next, by using a chromium target on the sputtering target, argon gas, Mixed gas of nitrogen and oxygen (Ar: 30% by volume, N2: 35 vol%, 〇2: 35 vol%) is reactively sprayed in an atmosphere to form an anti-reflection containing oxygen and nitrogen in chromium with a film thickness of 20 nm. Layer. As a result, a light-shielding layer and an anti-reflection layer having a total film thickness of 55 nm are formed on a light-transmitting substrate. In addition, the light-shielding film in the blank mask is in a laminated structure of the light-shielding layer and the anti-reflection layer thereon, and the optical density f· at an exposure wavelength of I93 nm is, for example, 3.0 or more. The reflectance at the exposure wavelength of 193 nm can be suppressed as low as 16%. Further, it is 18% for the 275 nm wavelength of the mask defect inspection wavelength, and there is no problematic reflectance even when the inspection is performed. Next, in order to improve the adhesion of the photoresist film formed on the light-shielding film, the above-mentioned blank mask is baked at 1 60 ° C in consideration of the type of photoresist. Secondly, it is formed on the above-mentioned blank mask. The film thickness of 15 Onm is a chemically amplified photoresist electron beam photoresist film (CAR-FEP171 manufactured by Fujifilm Electronic Materials Co., Ltd.). The formation of the photoresist film is spin-coated using a spinner (rotary coating device). After the photoresist film is applied, a prebaking treatment at 130 ° C is performed. Next, the photoresist film formed on the blank mask is subjected to an electron beam drawing device to perform a 45 nm half in the equivalent device. Pitch After the pattern is drawn, the photoresist pattern is formed by a predetermined development liquid. Next, along the photoresist pattern, dry etching of the anti-reflection layer is first performed to form an anti-reflection layer pattern. A mixed gas of Cl2 and 02 is used ( Cl2: 〇2 = 4 : 1) As the dry etching gas at this time. 200921269 Next, the light-shielding layer is formed by dry etching using the above-mentioned anti-reflection layer pattern and photoresist pattern as a mask. SF6 and He are used. The mixed gas is used as a dry etching gas at this time. Next, the remaining photoresist pattern is peeled off to obtain a photomask. The c D loss (c D error) of the formed light-shielding film pattern (offset of the measured line width with respect to the design line width) is as small as 20 nm. The pattern precision of the light-shielding film pattern on the mask is also good as designed. . By calculating the software (for example, the EM-set fifth edition), for example, optical conditions (λ = 139 nm, NA = 1 _ 3, the reticle EL 本 of the present embodiment obtained as above is obtained. In the method, the result of obtaining the mask EL of the present embodiment was as large as that of the mask EL of the comparative example described later. Incidentally, it is within the range of nS1 and k^2.5. Therefore, by using high In the case where the photomask is used to perform pattern transfer on a semiconductor substrate, the exposure apparatus of the NA exposure method can sufficiently accommodate the offset even if the focus position is shifted by the influence of the depth of focus. As a result, it is possible to form a fine pattern corresponding to a half pitch of 45 nm on a semiconductor substrate with high precision as designed. (Example 2) A light-transmitting substrate composed of the same synthetic quartz glass as in Example 1. In the argon (Ar) atmosphere, a mixed target of molybdenum (Mo) and bismuth (Si) is used on the sputtering target using a vane type sputtering apparatus (Mo: Si = 3: 97 at%). By sputtering (DC spraying), the film thickness is 33nm, and molybdenum and niobium are the main structures. The light-shielding layer of the element was formed. Then, the heating place 200921269 was treated for 3 hours at 5 〇〇. 3. Next, an anti-reflection layer was formed on the light-shielding layer in the same manner as in Example 1 to prepare a blank mask. The blank mask of the example has an optical density of 3:00 nm or more at an exposure wavelength of 3:00 nm. Further, the reflectance at the exposure wavelength of 139 nm is suppressed to as low as 19%. The blank mask thus obtained is used, The photomask was produced in the same manner as in Example 1. Even in the present embodiment, the c D loss (CD error) of the formed light-shielding film pattern (offset from the measured line width with respect to the design line width) was as small as 20 nm. The pattern accuracy of the light-shielding film pattern on the photomask was also as good as that of the design. The same as in Example 1, the result of the EL値 of the photomask of the present example was as high as that of the light of the comparative example described later. The cover EL値 is a large 値. In addition, it is in the range of n SI, k 2 2.5. Therefore, by using the exposure apparatus using the high NA exposure method, the reticle of the present embodiment is used on the semiconductor substrate. In the case of pattern transfer, even if it is subjected to focus The influence of the depth shifts the focus position, and the offset can be sufficiently tolerated. The result is that a fine pattern corresponding to a half pitch of 45 nm can be formed on the semiconductor substrate with high precision as designed. (Example 3) On a light-transmissive substrate composed of the same synthetic quartz glass as in Example 1, a vane type sputtering apparatus was used, and a mixed target of molybdenum (Mo) and bismuth (Si) was used on the sputtering target. (Mo: Si = 5: 95 at%), in an atmosphere of a mixture of argon (Ar) and oxygen and nitrogen (Ar: vol%, 〇2: 10 vol%, -20-200921269 N2: 80 vol%) In the gas, an inner anti-reflection film containing oxygen and nitrogen in molybdenum and niobium having a film thickness of 10 nm was formed by thermal spraying (DC sputtering). Next, on the inner anti-reflection film, a light-shielding layer and an anti-reflection layer were formed in the same manner as in the first embodiment to form a blank mask. However, the thickness of the light shielding layer of this embodiment was 35 nm, and the thickness of the antireflection layer was 20 nm. The blank mask of this embodiment has an optical density of 3.0 or more at an exposure wavelength of 193 nm. Further, the reflectance of the surface of the light-shielding film (the surface of the anti-reflection layer) at the exposure wavelength of 193 nm can be suppressed as low as 16%. Then, it is preferable to suppress the reflectance of the inner surface side of the blank mask to as low as 25 %, in particular, the pattern transfer by the exposure apparatus using the high NA exposure method. A reticle was produced in the same manner as in Example 1 using the blank mask thus obtained. That is, the photoresist film formed on the blank mask is subjected to pattern drawing corresponding to a half pitch of 45 nm by using an electron beam drawing device, and then developed to form a photoresist pattern. Next, in the same manner as in the first embodiment, the resist pattern was first subjected to dry etching of the antireflection layer to form a pattern of the antireflection layer. Next, the anti-reflection layer pattern and the photoresist pattern are used as a stop, and the light-shielding layer and the inner-surface anti-reflection film are dry-etched to form a pattern of the light-shielding film and the inner-surface anti-reflection film. Next, the remaining photoresist pattern is peeled off to obtain a photomask. Even in this embodiment, the CD loss (CD error) of the formed light-shielding film pattern (the unevenness of the measured line width with respect to the design line width) is as small as 20 nm, and the pattern precision of the light-shielding film pattern on the mask is also Good as designed. In the same manner as in the first embodiment, the result of E L 光 of the mask of the present embodiment was as high as -21 - 200921269. This 値 is a large 値 compared with the reticle EL 比较 of the comparative example described later. Incidentally, it is in the range of n S 1 and k 2 2.5. Therefore, by using the exposure apparatus of the high NA exposure method, in the case of performing pattern transfer on the semiconductor substrate using the photomask of the present embodiment, even if the focus position is shifted due to the influence of the depth of focus, it is sufficient The offset is affected, and as a result, a fine pattern equivalent to a half pitch of 45 nm can be formed on the semiconductor substrate with high precision as designed. (Comparative Example 1) A vane type sputtering apparatus was used on a light-transmitting substrate composed of the same synthetic quartz glass as in Example 1, and a mixed target of molybdenum (Mo) and bismuth (Si) was used for the sputtering target. (Mo: Si = 7: 93 atom%), and a light-shielding layer having a thickness of 42 nm and mainly composed of molybdenum and niobium was formed by sputtering (DC shot) in an argon (Ar) atmosphere. . Next, an anti-reflection layer was formed on the light-shielding layer in the same manner as in Example 1 to produce a blank mask. However, the film thickness of the antireflection layer of this comparative example was 2 0 n m. The blank mask of the comparative example had an optical density of 3.0 or more at an exposure wavelength of 193 nm. Further, the reflectance in the exposure wavelength I93 nm can be suppressed to as low as 14%. A reticle was produced in the same manner as in Example 1 using the blank mask thus obtained. In the same manner as in Example 1, the EL 光 of the photomask of the comparative example in which the yttrium content in the light-shielding film was 7 atom% was found to be low. Since the ruthenium and the light-shielding film have a Mo content of 6 atom% or less, the photomasks EL値-22 - 200921269 of the above-described respective embodiments are relatively small, and thus the photomask is used by using an exposure apparatus using a high-temperature exposure method. At the time of pattern transfer on a semiconductor substrate, 'the influence of the depth of focus of the optical system cannot be tolerated'. It is difficult to form a fine pattern corresponding to a half pitch of 45 nm on the semiconductor substrate with high precision as designed. (Comparative Example 2) A vane type sputtering apparatus was used on a light-transmissive substrate made of the same synthetic quartz glass as in Example 1, and a mixed target of molybdenum (Mo) and bismuth (Si) was used for the sputtering target. (Mo: Si = 7: 93 atom%) in an atmosphere of a mixed gas of Ar (Ar) and nitrogen and oxygen (Ar: 1% by volume, N2: 80% by volume, 02: 1% by volume) An inner anti-reflection film containing oxygen and nitrogen in molybdenum and niobium having a film thickness of 1 〇 nm is formed by sputtering (DC sputtering). Next, on the inner anti-reflection film, a vane type sputtering apparatus is used in the same manner, and a mixed target of molybdenum (Mo) and bismuth (Si) is used on the thermal spraying target (Mo: Si = 7: 93 atom%). In a argon gas (Ar) atmosphere, a light-shielding layer having a thickness of 42 ηηm and having molybdenum and rhenium as main constituent elements is formed by thermal spraying (DC thermal spraying). Next, an anti-reflection layer was formed on the light-shielding layer in the same manner as in Example 1 to produce a blank mask. However, the film thickness of the antireflection layer of this comparative example was 20 n. The blank mask of this comparative example has an optical density of 3.0 or more at an exposure wavelength of 193 nm. Further, the reflectance in the exposure wavelength of 139 nm can be suppressed to as low as 14%. Then, the reflectance on the inner surface side of the blank mask can be suppressed to as low as 22%. Using the blank mask thus obtained, a light -23-200921269 cover was produced in the same manner as in the third embodiment. In the same manner as in the first embodiment, the E L of the photomask of the comparative example was obtained, and the knot $ was low. Since the enamel and the reticle EL of the above-described embodiments in which the Mo content is 6 atom% & τ in the light-shielding film is relatively small, the reticle is used, and the illuminating device using the yttrium exposure method is used for the semiconductor. When the pattern is transferred by the reverse pattern, the influence of the depth of focus of the optical system cannot be tolerated, and a fine pattern equivalent to 4 5 nm _ | t5 is formed on the semiconductor substrate with high precision as designed. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing an m stomach of an embodiment of a blank mask of the present invention. Figure 2 is a diagram showing the stomach and stomach of the reticle manufacturing step using a blank mask. [Main component symbol description] 1 Translucent substrate 2 Light blocking film 3 Light blocking film 2 a Light blocking film pattern 3a Light resistance pattern 10 Empty white light cover 20 Light cover