TW201017328A - Multi-tone photomask, photomask blank, and pattern transfer method - Google Patents
Multi-tone photomask, photomask blank, and pattern transfer method Download PDFInfo
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- TW201017328A TW201017328A TW098132359A TW98132359A TW201017328A TW 201017328 A TW201017328 A TW 201017328A TW 098132359 A TW098132359 A TW 098132359A TW 98132359 A TW98132359 A TW 98132359A TW 201017328 A TW201017328 A TW 201017328A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
- H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
- H01L21/0274—Photolithographic processes
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
- G03F1/54—Absorbers, e.g. of opaque materials
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
- G03F1/54—Absorbers, e.g. of opaque materials
- G03F1/58—Absorbers, e.g. of opaque materials having two or more different absorber layers, e.g. stacked multilayer absorbers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/033—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers
- H01L21/0334—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers characterised by their size, orientation, disposition, behaviour, shape, in horizontal or vertical plane
- H01L21/0337—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers characterised by their size, orientation, disposition, behaviour, shape, in horizontal or vertical plane characterised by the process involved to create the mask, e.g. lift-off masks, sidewalls, or to modify the mask, e.g. pre-treatment, post-treatment
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Abstract
Description
201017328 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種多色調光罩、光罩基底及圖案轉印方 法等。 【先前技術】 近年來，於大型FPD(Flat Panel Display，平板顯示器）用 光罩之領域中，嘗試使用具有半透光性區域（所謂之灰色 調部）之多色調光罩（所謂之灰色調光罩）而削減光罩數量 (例如’參照月刊 FPD Intelligence、p.3 1-35、1999 年 5 月）。 此處，如圖11(1)及圖12(1)所示，多色調光罩於透光性 基板5上具有將曝光之光遮蔽之遮光部1、使曝光之光透過 之透光部2、以及使曝光之光之一部分透過的半透光部3。 半透光部3係用以獲得遮光部與透光部之中間透射率之區 域，例如係如圖11 (1)所示之形成有具有遮光部與透光部之 中間透射率之半透光膜3a'的區域，或者係如圖12(1)所示 之^^成有使用（搭載）多色調光罩而進行圖案轉印之大型 FPD用曝光機之解像極限以下的微細遮光圖案3a、及微細 透射部3b(所謂之灰色調圖案）之區域。形成半透光部3之目 的在於.降低透過該等區域之曝光之光的透射量，以降低 該區域之照射量’將與相關區域相對應之光阻劑顯影之後 所減少之膜厚控制為所期望之值。 ^將大型多色調光罩搭載於鏡面投影方式、或使用有透 鏡之透鏡投影方式之大型曝光裝置而使用之情形，透過半 143513.doc 201017328201017328 VI. Description of the Invention: [Technical Field] The present invention relates to a multi-tone mask, a mask base, a pattern transfer method, and the like. [Prior Art] In recent years, in the field of large-scale FPD (Flat Panel Display) reticle, attempts have been made to use a multi-tone mask having a semi-transparent region (so-called gray tone portion) (so-called gray tone) The mask is reduced by the number of masks (for example, 'Ref. Monthly FPD Intelligence, p. 3 1-35, May 1999). Here, as shown in FIGS. 11(1) and 12(1), the multi-tone mask has a light-shielding portion 1 that shields the exposed light, and a light-transmitting portion 2 that transmits the exposed light to the light-transmitting substrate 5. And a semi-transmissive portion 3 that transmits a portion of the exposed light. The semi-transmissive portion 3 is used to obtain a region of intermediate transmittance between the light-shielding portion and the light-transmitting portion. For example, as shown in FIG. 11 (1), a semi-transmissive light having an intermediate transmittance of the light-shielding portion and the light-transmitting portion is formed. As shown in Fig. 12 (1), the region of the film 3a' is a fine light-shielding pattern 3a which is equal to or lower than the resolution limit of the large-sized FPD exposure machine which is patterned by using a multi-tone mask. And a region of the fine transmissive portion 3b (so-called gray tone pattern). The purpose of forming the semi-transmissive portion 3 is to reduce the amount of light transmitted through the exposed regions to reduce the amount of exposure of the region, and to reduce the film thickness after the development of the photoresist corresponding to the relevant region is The expected value. ^When a large multi-tone mask is mounted on a mirror projection method or a large exposure apparatus using a lens projection method with a lens, it is transmitted through a half 143513.doc 201017328
透光部3的曝光之光整體之曝光量不足，因此，對於經由 該半透光部3而曝光之正型光阻劑而言，僅是膜厚變薄， 且會殘留於基板上。亦即’因曝光量之差異，於與通常之 遮光部1相對應之部分、及與半透光部3相對應之部分，光 阻劑相對於顯影液之溶解性產生差異，因此顯影後之光阻 劑形狀如圖Η⑺及圖12⑺所示，與通常之遮光部i相對應 之部分1’例如約為1 μιη，與半透光部3相對應之部分3,例如 約為0.4〜0·5 μπι ’與透光部2相對應之部分則成為無光阻劑 之部分2’。而且’於無光阻劑之部分2·進行被加工基板之 第1蝕刻’藉由灰化等而除去與半透光部3相對應之較薄之 部分3’之光阻劑，於該部分進行第2蝕刻，藉此，利用^固 光罩而實施先前由2個光罩實施之步驟，從而削減光罩數 量。 【發明内容】Since the exposure amount of the entire light of the light-transmitting portion 3 is insufficient, the positive-type photoresist exposed through the semi-transmissive portion 3 is thinned only on the substrate and remains on the substrate. That is, 'the difference between the amount of exposure, the portion corresponding to the normal light-shielding portion 1 and the portion corresponding to the semi-transmissive portion 3, the solubility of the photoresist with respect to the developer is different, so that after development The shape of the photoresist is as shown in Fig. 7(7) and Fig. 12(7), and the portion 1' corresponding to the usual light-shielding portion i is, for example, about 1 μm, and the portion 3 corresponding to the semi-light-transmitting portion 3 is, for example, about 0.4 to 0. The portion corresponding to the light transmitting portion 2 of 5 μm is formed as a portion 2' of no photoresist. Further, in the portion 2 where no photoresist is applied, the first etching of the substrate to be processed is performed, and the thin portion 3' corresponding to the semi-transmissive portion 3 is removed by ashing or the like, in which the photoresist is removed. By performing the second etching, the steps previously performed by the two masks are performed by the fixing mask, and the number of masks is reduced. [Summary of the Invention]
然而，用以製造微處理器、半導體記憶體、系統LSI (Large Scale Integration，大型積體電路）等之半導體裝置 之LSI用光罩相對較小，最大僅為6吋見方左右，多數情況 下，其搭載於步進（單步投影曝光）方式之縮小投影曝光裝 置而使用。又’ LSI用光罩中，自藉由透鏡系統而排除色 差及藉此提高解像性之觀點考慮’使用單色之曝光之光。 與該LSI用光罩相關之單色之曝光波長之短波長化，係朝 超高壓水銀燈之g線（436 nm)及i線（365 nm)、KrF準分子雷 射（248 nm)、ArF準分子雷射（193 nm)發展。 又’用以製造LSI用光罩之小型遮罩基底需要高蝕刻精 143513.doc 201017328 度，因此，藉由乾式姓刻而使形成於遮罩基底上之薄媒圖 案化。 相對於此，FPD用大型光罩相對較大，例如為33〇 mm><450 mm至1220 mmX1400 mm，多數情況下，其搭載 於鏡面投影方式或使用有透鏡之透鏡投影方式之曝光裝置 而使用。又，當將FPD用大型光罩搭載於鏡面投影（基於掃 描曝光方式之等倍投影曝光）方式之曝光裝置而使用之情 形’（I)由於僅利用反射光學系統而經由光罩進行曝光，故 因介設有如LSI用光罩之透鏡系統而產生之色差不會成為 問題；以及（II)目前’雖擔心多色波曝光之影響（因透射光 或反射光而產生之干涉或色差之影響等），但可確保比單 色波曝光更大之曝光光強度之多色波曝光於综合生產方面 較有利，因此，利用超高壓水銀燈之i〜g線之寬頻帶而實 施多色波曝光。又，即便當將FPD用大型光罩搭載於透鏡 方式之大型曝光裝置而使用之情形，根據上述（H)所記載 之理由[仍同樣地實施多色波曝光。才复數個》皮長之曝光 (多色波曝光）處理之優點在於：與單一波長之曝光（單色波 曝光)之情形相比較’曝光光強度可更大。例如，與僅利 用i線或8線之單色波曝光相比較，當利用包含^線在内之 自i線遍及g線之波長帶之光而 大。因此，可提高裝置之生產 進行曝光時，曝光光強度較 性。又，例如’於多數情況 下FPD裝置等之大型之顯示裝置係利用等倍曝光法而製 造。與LSI裝置等之製造中所使用之縮小曝光法相比較， 等倍曝光法具有如下優點：因照射至裝置面之曝光之光的 143513.doc 201017328 入射強度較小，故而可藉由利用複數個波長而彌補照射至 裝置面之曝光之光的入射強度。 又，FPD用大型光罩之製造中，難以製作大型之乾式蝕 刻裝置，即冑已製成該大型之乾式飯刻裝1，價格亦非常 ； 高，且技術上難以實現均一之蝕刻。因此，就用以製造 FPD用大型光罩之大型遮罩基底而言’多數情況下，重視 ' 成本方面及生產量而採用使用有蝕刻液之濕式蝕刻，使形 成於遮罩基底上之薄膜圖案化。 近年來，FPD用大型多色調光罩之需求精度（規格值）變 得嚴格。與此同時，業者亦期望削減成本。 因此，本發明者等人關於FpD用大型多色調光罩基底及 光罩，就如下課題進行了檢討，該課題之目的在於，於藉 由濕式钱刻而於半透光膜及遮光膜上實施圖案化之情形， 滿足變得嚴格之需求精度（規格值）。 結果發現難以同時滿足如下三個方面，即， 馨 （）抑制半透光膜之遍及丨線〜g線之波長帶之透射率變化 量； (2) 將透過半透光膜之曝光之光的透射率調整為所期望 .之值（尤其是容易進行微調整）；以及 (3) 可採用缺陷少之製程。 以下’對於上述情況進行詳細說明。 首先’作為前提，使用濕式蝕刻而製作之FPD用大型多 色調光罩中之遮光膜通常係使用Cr系遮光膜。 於將MoSiN用作半透光膜之FpD用大型多色調光罩基底 143513.doc 201017328 及光罩中，可使用自基板侧起具有基板\肘〇3丨>^半透光膜\ Cr系遮光膜之積層構造之光罩基底（先前例1)。此時，對於However, LSI reticle for manufacturing semiconductor devices such as microprocessors, semiconductor memories, and system LSIs (Large Scale Integration) is relatively small, and is only about 6 吋 square, and in most cases, It is used in a step-down (single-step projection exposure) reduction projection exposure apparatus. Further, in the LSI photomask, it is considered to use a single-color exposure light from the viewpoint of eliminating the chromatic aberration by the lens system and thereby improving the resolution. The short-wavelength of the single-color exposure wavelength associated with the LSI reticle is toward the g-line (436 nm) and i-line (365 nm) of the ultra-high pressure mercury lamp, KrF excimer laser (248 nm), ArF Molecular laser (193 nm) development. Further, the small mask substrate for manufacturing the LSI photomask requires a high etching precision of 143513.doc 201017328 degrees, so that the thin film formed on the mask substrate is patterned by the dry type. In contrast, a large reticle for FPD is relatively large, for example, 33 〇 mm >< 450 mm to 1220 mm X 1400 mm, and in many cases, it is mounted on a mirror projection method or an exposure apparatus using a lens projection method with a lens. use. In addition, when the FPD is mounted on a large-area reticle by an exposure apparatus of a mirror projection (a double projection exposure based on a scanning exposure method), (I) exposure is performed via a reticle by using only a reflection optical system, The chromatic aberration caused by the lens system such as the LSI reticle is not a problem; and (II) the current 'despite the influence of the multi-color wave exposure (the influence of interference or chromatic aberration due to transmitted light or reflected light, etc.) However, it is advantageous to ensure that the multi-color wave exposure of the exposure light intensity larger than that of the monochromatic wave exposure is advantageous in terms of integrated production. Therefore, multi-color wave exposure is performed by using the wide band of i to g lines of the ultrahigh pressure mercury lamp. Further, even when the FPD is mounted on a large-sized exposure apparatus using a large-sized photomask, the multi-color wave exposure is performed in the same manner as described in the above (H). The advantage of only a plurality of exposures (multicolor wave exposure) is that the exposure light intensity can be made larger than in the case of single wavelength exposure (monochrome exposure). For example, compared with the monochromatic or 8-line monochromatic wave exposure, the light from the wavelength band of the g-line from the i-line including the ^ line is large. Therefore, it is possible to improve the intensity of the exposure light when the device is produced for exposure. Further, for example, in many cases, a large display device such as an FPD device is manufactured by a double exposure method. Compared with the reduced exposure method used in the manufacture of an LSI device or the like, the equal-time exposure method has the advantage that the incident light is 143513.doc 201017328 which is irradiated to the device surface, so that a plurality of wavelengths can be utilized by using a plurality of wavelengths The incident intensity of the light that is exposed to the exposure of the device surface is compensated. Further, in the manufacture of a large-sized photomask for FPD, it is difficult to manufacture a large-sized dry etching apparatus, that is, the large-sized dry rice engraving apparatus 1 has been manufactured, and the price is also very high, and it is technically difficult to achieve uniform etching. Therefore, in the case of a large-sized mask substrate for manufacturing a large-sized photomask for FPD, in many cases, attention is paid to cost and throughput, and a wet etching using an etching solution is used to form a film formed on the mask substrate. Patterned. In recent years, the demand accuracy (specification value) of FPDs for large multi-tone masks has become strict. At the same time, the industry also expects to cut costs. Therefore, the inventors of the present invention have reviewed the following problems regarding a large-sized multi-tone mask base and a photomask for FpD, and the object of the present invention is to deposit a semi-transparent film and a light-shielding film by wet etching. In the case of patterning, the demand accuracy (specification value) that becomes strict is satisfied. As a result, it has been found that it is difficult to simultaneously satisfy the following three aspects, namely, the inhibition of the transmittance of the semi-transmissive film across the wavelength band of the 丨 line to the g line; (2) the light that is transmitted through the semi-transmissive film. The transmittance is adjusted to a desired value (especially for easy fine adjustment); and (3) a process with less defects can be used. The following will be described in detail. First, as a premise, a light-shielding film for a large-sized multi-tone mask for FPD produced by wet etching is usually a Cr-based light-shielding film. In the large-scale multi-tone mask substrate F153 for immersing MoSiN as a semi-transmissive film, 143513.doc 201017328 and a reticle, it is possible to use a substrate/elbow 3 from the substrate side. A reticle substrate of a laminated structure of a light-shielding film (previously Example 1). At this time, for
MoSiN半透光膜而言，其i線_g線間之透射率變動相對較 大’但用以獲得特定之透射率之膜厚相對較厚（例如約 20〜35 nm) ’因此’容易藉由膜厚而調整及控制透射率。 又，當將MoSiN用作半透光膜之情形，可採用先形成半透 光膜（圖10(1))及後形成半透光膜（圖10(2))之兩種製程。 於將CrN用作半透光膜之FPD用大型多色調光罩基底及 光罩（先前例2)中，對於CrN半透光膜而言’其丨線^線間之 透射率變動相對較小，但用以獲得特定之透射率之膜厚相 對較薄（例如約10 nm以下之非常薄之厚度），因此，難以 藉由膜厚而調整或控制透射率。又，CrN半透光膜幾乎不 具有與Cr系遮光膜之蝕刻選擇性，因此，必需首先使心系 遮光膜成膜並使之圖案化’其後’使CrN半透光膜成膜並 使之圖案化（必需採用所謂之後形成半透光膜之製程）。於 後形成半透光膜之製程之情料，必需將成膜與使所形成 之膜圖案化之-系列步驟分成2次進行，因此與先形成半 透光膜之製程相比較，缺陷增加。 如上所述，尚未提出具有先前例1及先前例2該兩者之優 點且可、;肖除兩者之缺點之技術。亦即，尚未提出可同時滿 足上述（1)〜(3)之技術。 本發明係關於一種FPD用大型多色調光罩基底及光罩， ，、目的在於提供-種可同時滿足以下之 ⑴抑制半透光媒之遍及i線〜以 ()：技術。 及長帶之透射率變… 143513.doc 201017328In the MoSiN semi-transmissive film, the transmittance between the i-line and the g-line varies relatively 'but the film thickness to obtain a specific transmittance is relatively thick (for example, about 20 to 35 nm). The transmittance is adjusted and controlled by the film thickness. Further, when MoSiN is used as the semi-transmissive film, two processes of forming a semi-transmissive film (Fig. 10 (1)) and then forming a semi-transparent film (Fig. 10 (2)) can be employed. In the large multi-tone mask base and the photomask for the FPD using CrN as a semi-transmissive film (previous example 2), the transmittance variation between the turns of the CrN semi-transmissive film is relatively small. However, the film thickness for obtaining a specific transmittance is relatively thin (for example, a very thin thickness of about 10 nm or less), and therefore, it is difficult to adjust or control the transmittance by the film thickness. Further, since the CrN semi-transmissive film hardly has etching selectivity with the Cr-based light-shielding film, it is necessary to first form a film of the core-based light-shielding film and pattern it to "form" to form a CrN semi-transmissive film. The patterning (required to use a process of forming a semi-transmissive film later). In the subsequent process of forming the semi-transmissive film, it is necessary to divide the film formation and the series of steps for patterning the formed film into two, so that the defects are increased as compared with the process of forming the semi-transmissive film first. As described above, the technique of the prior art 1 and the prior example 2 has not been proposed and can be used to eliminate the disadvantages of both. That is, the technology of the above (1) to (3) has not been proposed yet. The present invention relates to a large-sized multi-tone mask base and a photomask for FPD, and aims to provide the following ones: (1) Suppressing a semi-transmissive medium throughout the i-line to (): technology. And the transmittance of the long belt becomes... 143513.doc 201017328
(2) 將透過半透光臈之曝光之 (尤其是容易進行微調整）。 (3) 可採用缺陷少之製程。 光的透射率調整為所期 望之值 結=者等人為解決上述問題而進行了銳意研究開發(2) Exposure through a semi-transparent ( (especially easy to fine-tune). (3) A process with few defects can be used. The transmittance of light is adjusted to the desired value. No one has made a research and development to solve the above problems.
(:)將半透光臈設為相對於遍及丨線〜§線之波長帶之 光的透射率光譜互不相同之2層以上之半透光骐 膜，藉此 曝光之 的積層 ⑼包含上述積層膜之半透光膜係藉由2層以上之半透光膜 之積層’而可恰當地控制透過相對於包含上述積層膜之半 透光膜且遍及i線〜g線之波長帶的曝光之光之透射率變化 量；且(:) The semi-transparent 臈 is a semi-transparent ruthenium film having two or more layers of transmittance spectra of light in a wavelength band extending over the 丨 line to the § line, and the exposed layer (9) includes the above The semi-transmissive film of the laminated film is capable of appropriately controlling the exposure through the wavelength band of the semi-transmissive film including the laminated film and the i-line to the g-line by the laminate of two or more semi-transmissive films. The amount of change in transmittance of light; and
包含上述積層臈之半透光膜係藉由2層以上之半透光膜 之積層’而可恰當地控制透過包含上述積層帛之半透光膜 的曝光之光的透射率。藉此，本發明者等人發現可獲得可 同時滿足上述（1)〜(3)之；FPD用大型多色調光罩基底及光 罩。 進而’本發明者發現，即便構成上述積層膜之各半透光 膜之材料相同，亦會由於各半透光膜之膜厚而可獲得抑制 遍及1線〜g線之波長帶之透射率變化量的效果，或無法獲 得該效果。據此，本發明者發現： (111)對於以「包含上述積層膜之半透光膜係可藉由2層以上 之半透光膜之積層’而控制透過相對於包含上述積層膜之 143513.doc -9- 201017328 半透光膜且遍及i線〜g線之波長帶的曝光之光的透射率變 化量（抑制為所期望之值），且 包含上述積層膜之半透光膜係可藉由2層以上之半透光 膜之積層，而控制透過包含上述積層膜之半透光膜的曝光 之光之透射率（控制為所期望之值）」之方式而構成上述積 層膜的各半透光膜之材料及膜厚進行選擇（調整），藉此， 可獲得可同時滿足上述（1)〜(3)之FPD用大型多色調光罩基 底及光罩’從而完成本發明。 本發明之多色調光罩、光罩基底及圖案轉印方法具有如 下構成。 (構成1) 一種光罩基底，其特徵在於：其係用以製作多色調光罩 者，該多色調光罩係於透光性基板上，依序具有使曝光之 光之一部分透過之半透光膜及將曝光之光遮蔽之遮光膜， 且藉由對上述半透光膜及上述遮光膜分別實施圖案化而形 成有使曝光之光透過之透光部、使曝光之光之一部分透過 之半透光部、以及將曝光之光遮蔽之遮光部， 上述半透光膜包含相對於遍及i線〜g線之波長帶之曝光 之光的透射率光譜互不相同之2層以上之半透光膜的積層 膜， 包含上述積層膜之半透光膜係藉由2層以上之半透光膜 之積層’而控制相對於透過包含上述積層膜之半透光膜且 遍及i線〜g線之波長帶之曝光之光的透射率變化量，且 包含上述積層膜之半透光膜係藉由2層以上之半透光膜 143513.doc •10- 201017328 之積層’而控制透過包含上述積層骐之半透光膜的曝光之 光之透射率。 (構成2) 如構成1之光罩基底，其特徵在於： 構成上述積層膜之至少一方之半透光膜係具有抑制遍及 i線〜g線之波長帶之透射率變化量之功能的膜，且 藉由調整構成上述積層膜之至少一方之半透光膜的膜 厚，而將透㉟包含上述積層m之半透光膜的曝光之光的透 射率調整為所期望之值。 (構成3) 如構成1或2之光罩基底，其特徵在於： 包含上述積層膜之半透光臈之相對於遍及i線〜g線之波 長帶之曝光之光的透射率變化量為2 〇%以下。 (構成4) 如構成1至3中任一項之光罩基底，其特徵在於： 於透光性基板上依序積層半透光膜之積層膜、及 包含含有鉻之材料之遮光膜而成， 上述半透光膜之積層膜係依序積層包含含有鉻與氮之材 料之半透光膜、以及包含含有鉬與矽之材料或含有鉬、矽 及氮之材料的半透光膜而成。 (構成5) 一種多色調光罩，其特徵在於：於透光性基板上，依序 具有使曝光之光的一部分透過之半透光膜及將曝光之光遮 蔽之遮光膜，藉由對上述半透光膜及上述遮光膜分別實施 143513.doc -11- 201017328 圖案化’而形成有使曝光之光透過之透光部、使曝光之光 之一部分透過之半透光部、以及將曝光之光遮蔽之遮光 部， 上述半透光膜包含相對於遍及i線〜g線之波長帶之曝光 之光的透射率光譜互不相同之2層以上之半透光膜的積層 膜， 包3上述積層膜之半透光膜係藉由2層以上之半透光膜 之積層，而控制相對於透過包含上述積層膜之半透光膜且 遍及i線〜g線之波長帶之曝光之光的透射率變化量，且 包含上述積層膜之半透光膜係藉由2層以上之半透光膜 之積層，而控制透過包含上述積層膜之半透光膜之曝光之 光的透射率。 (構成6) 如構成5之多色調光罩’其特徵在於： 上述半透光部係於透光性基板上，形成有由積層構造之 半透光臈所構成之半透光部。 (構成7) 如構成5之多色調光罩，其特徵在於： 上述半透光部具有曝光之光的透射率不同之第丨半透光 部與第2半透光部，上述第！半透光部係於透光性基板上， 形成有僅由積層構造之半透光媒之下層膜所構成之半透光 部’上述第2半透光部係於透光性基板上，形成有由積層 構造之半透絲之下層膜及上層膜之積層膜所構成 杏.都。 143513.doc •12- 201017328 (構成8) 一種圖案轉印方法，其包括如下步驟： 使用構成5至7中任一 jf夕夕, Τ任項之夕色調光罩，且藉由遍 1線之波長帶的曝光之光， ：及線 }肝尤卓上所形成之多色調圖 案轉印至被轉印體上。The semi-transmissive film including the laminated germanium can appropriately control the transmittance of the light transmitted through the semi-transmissive film containing the laminated germanium by the layer ' of the two or more semi-transmissive films. Accordingly, the inventors of the present invention have found that a large-sized multi-tone mask base and a reticle for FPD can be obtained simultaneously satisfying the above (1) to (3). Further, the inventors have found that even if the materials of the semi-transmissive films constituting the laminated film are the same, the transmittance of the wavelength band across the 1 line to the g line can be suppressed due to the film thickness of each of the semi-transmissive films. The effect of the amount, or the effect cannot be obtained. Accordingly, the inventors have found that: (111) controlling the transmission by "the semi-transmissive film comprising the laminated film can be laminated by a semi-transmissive film of two or more layers" with respect to the 143513 containing the laminated film. Doc -9- 201017328 Semi-transmissive film and the amount of change in transmittance of light exposed to the wavelength band of the i-line to the g-line (suppressed to a desired value), and the semi-transmissive film system including the above laminated film can be borrowed The half of the laminated film is formed by controlling the transmittance of the exposed light transmitted through the semi-transmissive film including the laminated film (controlled to a desired value) by laminating two or more layers of the semi-transmissive film. The material and the film thickness of the light-transmissive film are selected (adjusted), whereby the large-sized multi-tone mask base for FPD and the mask "which can simultaneously satisfy the above (1) to (3) can be obtained, thereby completing the present invention. The multi-tone mask, the mask substrate and the pattern transfer method of the present invention have the following constitution. (Configuration 1) A reticle substrate, which is used for fabricating a multi-tone mask, which is attached to a light-transmitting substrate, and has a semi-transparent portion for partially transmitting the exposed light. a light-shielding film and a light-shielding film that shields the exposed light, and each of the semi-transmissive film and the light-shielding film is patterned to form a light-transmitting portion through which the exposed light is transmitted, and a portion of the exposed light is transmitted through a semi-transmissive portion and a light-shielding portion that shields the exposed light, wherein the semi-transmissive film includes two or more layers of transmissivity spectra of light that are exposed to light in a wavelength band extending from i to g lines. The laminated film of the light film, the semi-transmissive film including the laminated film is controlled by the layer of the semi-transmissive film of two or more layers, and is transmitted over the i-line to the g-line through the semi-transmissive film including the laminated film. The amount of change in transmittance of the exposed light in the wavelength band, and the semi-transmissive film including the laminated film is controlled to pass through the laminate of two or more layers of semi-transmissive film 143513.doc •10- 201017328 Exposure light of semi-transparent film Transmittance. (Structure 2) The light-shielding substrate of the configuration 1 is characterized in that the semi-transmissive film constituting at least one of the laminated films has a function of suppressing a change in transmittance of a wavelength band extending from the i-th to the g-line. Further, by adjusting the film thickness of the semi-transmissive film constituting at least one of the laminated films, the transmittance of the exposed light of the semi-transmissive film including the laminated layer m is adjusted to a desired value. (Structure 3) The reticle base of the first or second embodiment, wherein the amount of change in transmittance of the semi-transparent yttrium containing the laminated film with respect to the exposure light in the wavelength band from the i-th to the g-line is 2 〇% or less. (Attachment 4) The reticle base according to any one of the first to third aspect, wherein the laminated film of the semi-transmissive film and the light-shielding film containing the material containing chromium are sequentially formed on the light-transmitting substrate. The laminated film of the semi-transmissive film is a semi-transparent film comprising a material containing chromium and nitrogen, and a semi-transparent film comprising a material containing molybdenum and niobium or a material containing molybdenum, niobium and nitrogen. . (Configuration 5) A multi-tone mask characterized in that a semi-transmissive film that transmits a part of exposed light and a light-shielding film that shields exposed light are sequentially provided on the light-transmitting substrate. The semi-transmissive film and the light-shielding film are respectively patterned by 143513.doc -11-201017328, and a light-transmitting portion through which the exposed light is transmitted, a semi-transmissive portion through which a part of the exposed light is transmitted, and an exposure portion are formed. a light-shielding light-shielding portion, wherein the semi-transmissive film includes a laminated film of two or more semi-transmissive films having different transmittance spectra of light exposed in a wavelength band of i lines to g lines, and the package 3 The semi-transmissive film of the laminated film is controlled by a laminate of two or more semi-transmissive films to control the light transmitted through the wavelength band of the semi-transmissive film including the laminated film and extending over the i-th to g-line. The transmittance change amount, and the semi-transmissive film including the laminated film is controlled by a laminate of two or more semi-transmissive films to control the transmittance of light that is transmitted through the semi-transmissive film including the laminated film. (Configuration 6) The multi-tone mask of the fifth aspect is characterized in that the semi-transmissive portion is formed on a light-transmissive substrate, and a semi-transmissive portion composed of a semi-transparent enamel having a laminated structure is formed. (Configuration 7) The multi-tone mask of the fifth aspect, wherein the semi-transmissive portion has a second semi-transmissive portion and a second semi-transmissive portion having different transmittances of light to be exposed, the above-mentioned! The semi-transmissive portion is formed on the light-transmissive substrate, and the semi-transmissive portion formed by the underlying film of the semi-transmissive medium having a laminated structure is formed, and the second semi-transmissive portion is formed on the light-transmissive substrate. There is an apricot composed of a laminated film of a semi-transparent filament and a laminated film of an upper layer. 143513.doc • 12- 201017328 (Embodiment 8) A pattern transfer method comprising the steps of: using any of the jf eves of any of the constituents 5 to 7; The light of the exposure band of the wavelength band, and the multi-tone pattern formed on the line of the liver are transferred to the object to be transferred.
根據本發明’可提供—種可㈣滿足下述⑴〜(3)之FPD 用大型多色調光罩基底及光罩、以及其等之製造方法。According to the present invention, a large multi-tone mask substrate and a photomask for FPD satisfying the following (1) to (3), and a method of manufacturing the same can be provided.
❹ ⑴抑制半透光膜之遍及i線〜g線之波長帶之透射率變化 量。 (2) 將透過半透光膜之曝光之光的透射率調整為所期望之值 (尤其是容易進行微調整）。 (3) 可採用缺陷少之製程。 【實施方式】 以下，對本發明進行詳細說明。 本發明之特徵在於：其係多色調光罩、或用以製作該多 色調光罩之光罩基底，該多色調光罩係於透光性基板上， 依序具有使曝光之光的一部分透過之半透光膜及將曝光之 光遮蔽之遮光膜，且藉由對上述半透光膜及上述遮光膜分 別實施圖案化’而形成有使曝光之光透過之透光部、使曝 光之光之一部分透過之半透光部、以及將曝光之光遮蔽的 遮光部， i述半透光膜包含相對於遍及i線〜g線之波長帶的曝光 之光之透射率光譜互不相同之2層以上的半透光膜之積層 膜， M3513.doc •13· 201017328 包3上述積層膜之半透光膜係藉由2層以上之半透光膜 之積層，而控制相對於透過包含上述積層膜之半透光膜且 遍及1線〜g線之波長帶的曝光之光之透射率變化量且 包含上述積層膜之半透光膜係藉由2層以上之半透光膜 之積層，而控制透過包含上述積層膜之半透光膜的曝光之 光的透射率（構成1、構成5)。 根據上述構成1、構成5之發明，可提供可同時滿足下述 (1)〜(3)之FPD用大型多色調光罩基底及光罩、以及該等之 製造方法。 (1) 抑制半透光膜之遍及i線〜g線之波長帶之透射率變化 量； (2) 將透過半透光膜的曝光之光的透射率調整為所期望之值 (尤其是容易進行微調整）； (3) 可採用缺陷少之製程。 可以說，本發明之光罩基底及光罩如上所述，其特徵在 於：對於以「包含上述積層膜之半透光膜可藉由2層以上 之半透光膜之積層，而控制相對於透過包含上述積層膜之 半透光膜且遍及i線〜g線之波長帶的曝光之光之透射率變 化量（抑制為所期望之值），且 包含上述積層膜之半透光膜可藉由2層以上之半透光膜 之積層，而控制透過包含上述積層膜之半透光膜的曝光之 光的透射率（抑制為所期望之值）」之方式而構成上述積層 膜的各半透光膜之材料及膜厚進行選擇（調整）。 藉此，可獲得可同時滿足上述〇)〜(3)之FPD用大型多色 143513.doc 201017328 調光罩基底及光罩。 具體而言，例如，半透光膜係自基板側起積層有 CrNVM〇SiN之積層膜。當M〇SiN之膜厚恰當之情形（膜厚相 對較小之情形）’可獲得將遍及丨線〜g線之波長帶之透射率 ； 冑化量抑制為㈣以下之效果。X，可利用M〇SiN之臈厚 而對透射率進行微調整。相對於此，當MoSiN之膜厚不恰 • 當之情形（膜厚相對較大之情形），無法獲得抑制遍及丨線〜§ ^ 線之波長帶之透射率變化量之效果。 本發明之光罩基底及光罩之特徵在於： 構成上述積層膜之至少一方之半透光膜係具有抑制遍及 I線〜g線之波長帶之透射率變化量之功能的膜，且 藉由調整構成上述積層膜之至少一方之半透光膜的膜 厚，而將透過包含上述積層膜之半透光膜的曝光之光的透 射率調整為所期望之值（構成2)。 根據上述構成2之發明，可提供可同時滿足下述（1)〜(3) φ 之FPD用大型多色調光罩基底及光罩、以及其等之製造方 法。 (1) 抑制半透光膜之遍及i線〜g線之波長帶之透射率變化 量； (2) 將透過半透光膜的曝光之光的透射率調整為所期望之值 (尤其是容易進行微調整 (3) 可採用缺陷少之製程。 上述構成2之發明包含以下態樣。 (態樣1) 143513.doc -15- 201017328 S亥態樣1係利用如下兩種膜之積層膜而構成半透光膜之 態樣’上述兩種膜係：匕缘1線間之透射率變動相對較大， 但用以獲得特定之透射率之膜厚相對較厚，因此易於對透 射率進行調整、控制之膜；以及 i線-g線間之透射率變動相對較小，但用以獲得特定之透 射率之膜厚相對較薄，因此難以於對透射率進行調整、控 制之膜。 作為上述態樣1之具體例，例如可列舉利用自基板側起 積層有CrN\M〇SiN之積層膜而構成半透光膜之態樣。 (態樣2) 該痣樣2係利用如下兩種膜之積層膜而構成半透光膜之 態樣，上述兩種膜係：i線_§線間之透射率變動相對較小， 且用以獲得特定之透射率之膜厚相對較厚，因此易於對透 射率進行調整、控制之膜；以及 1線-g線間之透射率變動相對較小，但用以獲得特定之透 射率之膜厚相對較薄，因此難以對透射率進行調整、控制 之膜。 作為上述態樣2之具體例，例如可列舉利用自基板側起 積層有CrN\MoSi之積層膜而構成半透光臈之態樣。於該情 形時，可利用CrN膜、MoSi膜中之任一方之膜或雙方之膜 之膜厚而調整透射率。又，亦可根據M〇Si膜之成膜條件而 調整MoSi膜之透射率，藉此，調整包含積層膜之半透光膜 的透射率。進而，可利用MoSiN之膜厚而對透射率進行微 調整。 I435I3.doc -16 - 201017328 再者，於上述態樣卜2中，可將如下之膜設為下層（基 板側之層）’亦可設於上層（遮光膜側之層），該膜係1線_§ 線間之透射率變動相對較小，但用以獲得特定透射率之膜 厚相對較薄，因此難以對透射率進行調整、控制之膜。 ； 本發明之光罩基底及光罩中，對於包含積層膜之半透光 膜而言，以遍及i線〜g線之波長帶之透射率變化量為2〇% ‘ 以下為佳（構成3)。 _ 其原因在於用以滿足變得嚴格之需求精度（規格值）。 又，其原因在於，可大幅度地獲得藉由將半透光膜之遍及 1線〜g線之波長帶之透射率變化量抑制得較小而產生的效 果。 自同樣之觀點考慮，對於包含積層膜之半透光膜而言， 更好的是，遍及i線〜g線之波長帶之透射率變化量為15% 以下。 本發明之光罩基底及光罩中，對於構成上述積層膜之至 φ 少一方之半透光膜而言，包含相對於遍及i線〜g線之波長 T之曝光之光的透射率變化量（丨線〜g線之波長帶中之透射 率之最大值與最小值之差）宜為1 ·5%以下之材料。 作為此種材料，可列舉MoSi、CrN等。其中，自下述 (a)〜(d)等之方面考慮，最好的是CrN。 Ο)相對於遍及丨線〜g線之波長帶之曝光之光的透射率之 波長依存性較小。 (b)耐化學性（耐沖洗性）及耐光性優良。 (e)可控制蝕刻速度。 143513.doc -17- 201017328 (d)相對於他方之半透光膜（例如M〇SiN、MoSi等）之蚀刻 液’姓刻選擇性充分’因此’當對他方之半透光膜（例如 MoSiN、MoSi等）進行蝕刻之情形，半透光膜所受之損傷 較小。 本發明之光罩基底及光罩例如包含如下態樣，即，於透 光性基板上，依序積層有半透光膜之積層膜、及包含含有 鉻之材料之遮光膜而成， 上述半透光膜之積層膜係由包含含有鉻與氮之材料之半 透光膜、以及包含含有鉬與矽之材料、或含有鉬、矽及氮 之材料的半透光膜依序積層而成（構成4)。 本發明之光罩基底及光罩中，當使用包含自基板側起積 層有CrN\M〇SiN之積層膜之半透光膜之情形，可獲得以下 效果。 1) 藉由將MoSiN之膜厚設為恰當之厚度，可獲得將遍及匕線 〜g線之波長帶之透射率變化量抑制為1.5 %以下之效果。 2) 與使用CrN單層膜之情形（先前例2)相比較，易於調整、 控制為所期望之透射率，尤其容易對透射率進行微調整。 3) 可使用先形成半透光膜之製程； 4) 與使用MoSiN單層膜之情形（先前例丨）相比較，可使 MoSiN膜變薄，因此可縮短蝕刻時間。具體而言，與先前 例1相比較，膜厚約為丨/3，適量蝕刻時間約為丨/5。 5) 與MoSi系單層膜（河〇8丨、M〇sm等）相比較，於積層膜之 狀態下，薄片電阻較低。一般認為5^〇8丨系膜雖然為非導電 性，但可利用與下層接觸之CrN膜之穿遂效應而獲得導電 143513.doc -18- 201017328 性。 6)與MoSi系單層膜（MoSi、MoSiN等）相比較，耐光性、耐 化學性優良。CrN膜之耐光性•耐化學性亦優良，故而包 含積層膜之半透光膜之耐光性、耐化學性亦優良。 - 7)於自基板側起積層有半透光性之CrN膜（下層）、與其接 觸之半透光性之MoSi膜（上層）、以及與其接觸之心系遮光 •膜之積層構造中之各層之間，可獲得較高之蝕刻選擇比。 _ 本發明之光罩基底及光罩中，包含積層膜之半透光膜可 設為2層構造（雙層膜），亦可設為3層以上之多層構造（多層 膜）。 本發明中，構成積層膜之各半透光膜可設為含有金屬之 膜。 本發明中’包含積層膜之半透光膜於積層膜之狀態下， 宜呈現如下之導電性，即，電阻為薄片電阻值】kn/口以 下。 φ 本發明之光罩基底及光罩中，作為半透光膜之材質，宜 藉由選擇臈厚，使得當將透光部之透射率設為1〇〇%之情 形’可獲得透射率20〜60%左右（以40〜60%為佳）之半透過 性者，例如可列舉MoSi系材料、Cr化合物（Cr之氧化物、 氮化物、氮氧化物、氟化物等）、Si、W、A1等。Si、W、 A1等係由於其膜厚而可獲得較高之遮光性或半透過性之材 質。 此處半透光媒之材料並不限於由Mo與Si構成之MoSi 系材料’可列舉金屬及矽（MSi，其中Μ係M〇、Ta、W、 143513.doc -19- 201017328❹ (1) The amount of change in transmittance of the semi-transmissive film across the wavelength band from the i-line to the g-line is suppressed. (2) The transmittance of the light that has passed through the semi-transmissive film is adjusted to a desired value (especially, it is easy to perform fine adjustment). (3) A process with few defects can be used. [Embodiment] Hereinafter, the present invention will be described in detail. The invention is characterized in that it is a multi-tone mask or a mask base for fabricating the multi-tone mask, the multi-tone mask is attached to the light-transmissive substrate, and sequentially has a part of the exposed light transmitted through a semi-transmissive film and a light-shielding film that shields the exposed light, and each of the semi-transmissive film and the light-shielding film is patterned to form a light-transmitting portion through which the exposed light is transmitted, and the light to be exposed a part of the semi-transmissive portion and the light-shielding portion that shields the exposed light, and the semi-transmissive film includes different transmittance spectra of the exposed light with respect to the wavelength band of the i-line to the g-line. a laminated film of a semi-transparent film above the layer, M3513.doc •13· 201017328 The semi-transmissive film of the above laminated film is composed of a laminate of two or more semi-transmissive films, and is controlled to contain the above-mentioned laminated layer with respect to transmission. The semi-transmissive film of the film and the transmittance change amount of the exposed light in the wavelength band of the 1 line to the g line, and the semi-transmissive film including the laminated film is laminated by the semitransparent film of 2 or more layers, and Controlling exposure through a semi-transparent film comprising the above laminated film The light transmittance (configuration 1, configuration 5). According to the inventions of the above-described configuration 1 and 5, it is possible to provide a large-sized multi-tone mask base and a photomask for FPD which can satisfy the following (1) to (3), and a manufacturing method therefor. (1) suppressing the change in transmittance of the semi-transmissive film across the wavelength band of the i-line to the g-line; (2) adjusting the transmittance of the exposed light transmitted through the semi-transmissive film to a desired value (especially easy Make minor adjustments); (3) Processes with few defects can be used. It can be said that the reticle base and the reticle of the present invention are characterized in that "the semi-transmissive film including the laminated film can be laminated by a semi-transparent film of two or more layers, and the control is relative to a semi-transmissive film containing the semi-transmissive film of the laminated film and having a wavelength change of light exposed to a wavelength band of the i-line to the g-line (suppressed to a desired value), and the semi-transparent film including the laminated film can be borrowed The half of the laminated film is formed by laminating two or more layers of the semi-transmissive film and controlling the transmittance of the light that is transmitted through the semi-transmissive film including the laminated film (suppressed to a desired value). The material and film thickness of the light-transmissive film are selected (adjusted). Thereby, a large multicolor 143513.doc 201017328 dimming cover base and a reticle capable of satisfying the above 〇) to (3) can be obtained. Specifically, for example, the semi-transmissive film is a laminated film of CrNVM〇SiN laminated from the substrate side. When the film thickness of M 〇 SiN is appropriate (the case where the film thickness is relatively small), the transmittance of the wavelength band passing through the 丨 line to the g line is obtained, and the amount of bismuth is suppressed to (4) or less. X, the transmittance can be finely adjusted by using the thickness of M〇SiN. On the other hand, when the film thickness of MoSiN is not appropriate (in the case where the film thickness is relatively large), the effect of suppressing the change in the transmittance of the wavelength band across the 〜 line to the § ^ line cannot be obtained. The reticle base and the reticle of the present invention are characterized in that the semi-transmissive film constituting at least one of the laminated films has a function of suppressing a change in transmittance of a wavelength band extending from the I line to the g line, and The film thickness of the semi-transmissive film constituting at least one of the laminated films is adjusted, and the transmittance of the light that has passed through the semi-transmissive film including the laminated film is adjusted to a desired value (Configuration 2). According to the invention of the above configuration 2, it is possible to provide a large-sized multi-tone mask base and a photomask for FPD which can simultaneously satisfy the following (1) to (3) φ, and a method of manufacturing the same. (1) suppressing the change in transmittance of the semi-transmissive film across the wavelength band of the i-line to the g-line; (2) adjusting the transmittance of the exposed light transmitted through the semi-transmissive film to a desired value (especially easy Micro-adjustment (3) A process with few defects can be used. The invention of the above-mentioned composition 2 includes the following aspects: (Stage 1) 143513.doc -15- 201017328 S-like sample 1 uses a laminate film of the following two films The pattern of the semi-transmissive film is as follows: The transmittance of the two film systems is relatively large, but the film thickness for obtaining a specific transmittance is relatively thick, so that the transmittance is easily adjusted. The film under control and the transmittance change between the i-line and the g-line are relatively small, but the film thickness for obtaining a specific transmittance is relatively thin, so that it is difficult to adjust and control the transmittance. Specific examples of the aspect 1 include a laminate film in which CrN\M〇SiN is laminated from the substrate side to form a semi-transmissive film. (Section 2) The sample 2 uses the following two films. The film is laminated to form a semi-transmissive film, and the above two film systems are: i line _ § line The change in the transmittance is relatively small, and the film thickness for obtaining a specific transmittance is relatively thick, so that it is easy to adjust and control the transmittance; and the transmittance variation between the 1-line-g lines is relatively small, but A film having a relatively small film thickness to obtain a specific transmittance is difficult to adjust and control the transmittance. As a specific example of the second aspect, for example, a laminate in which CrN\MoSi is laminated from the substrate side is used. The film forms a semi-transparent 臈. In this case, the transmittance can be adjusted by using either the CrN film or the MoSi film or the film thickness of both films. The transmittance of the MoSi film is adjusted by the film formation conditions, whereby the transmittance of the semi-transmissive film including the laminated film is adjusted. Further, the transmittance can be finely adjusted by the film thickness of MoSiN. I435I3.doc -16 - 201017328 Further, in the above aspect 2, the following film may be set as the lower layer (layer on the substrate side) or may be provided on the upper layer (layer on the light shielding film side), and the film is 1 line _ § line Transmittance variation is relatively small, but used to achieve specific transmittance The film thickness is relatively thin, so that it is difficult to adjust and control the transmittance of the film. In the reticle substrate and the reticle of the present invention, the semi-transmissive film including the laminated film is spread over the i-line to the g-line. The amount of change in the transmittance of the wavelength band is 2%%. The following is preferable (construction 3). _ The reason is to satisfy the demand accuracy (standard value) which becomes strict. Moreover, the reason is that it can be obtained largely The effect of suppressing the amount of change in transmittance in the wavelength band of the semi-transmissive film over the 1 line to the g line is small. From the same viewpoint, for the semi-transparent film including the laminated film, Preferably, the transmittance change amount in the wavelength band of the i-line to the g-line is 15% or less. In the reticle base and the reticle of the present invention, the semi-transmissive film constituting the laminated film having a smaller φ includes a change in transmittance of light exposed to a wavelength T extending from the i-th to the g-line. (The difference between the maximum value and the minimum value of the transmittance in the wavelength band of the 丨 line to the g line) is preferably 1 % or less. As such a material, MoSi, CrN, etc. are mentioned. Among them, CrN is the most preferable from the viewpoints of (a) to (d) below. Ο) The wavelength dependence of the transmittance of the light exposed to the wavelength band across the 〜 line to the g line is small. (b) Excellent chemical resistance (washing resistance) and light resistance. (e) The etching rate can be controlled. 143513.doc -17- 201017328 (d) The etching solution of the semi-transparent film (such as M〇SiN, MoSi, etc.) is more selective than the other one. Therefore, it is a semi-transparent film (such as MoSiN). In the case of etching, MoSi, etc., the semi-transmissive film is less damaged. The reticle base and the reticle of the present invention include, for example, a laminated film in which a semi-transparent film is laminated on a light-transmitting substrate, and a light-shielding film containing a material containing chromium, The laminated film of the light-transmissive film is formed by sequentially laminating a semi-transparent film containing a material containing chromium and nitrogen, and a semi-transmissive film containing a material containing molybdenum and niobium or a material containing molybdenum, niobium and nitrogen ( Composition 4). In the case of the reticle base and the reticle of the present invention, when a semi-transmissive film comprising a laminated film of CrN\M〇SiN laminated from the substrate side is used, the following effects can be obtained. 1) By setting the film thickness of MoSiN to an appropriate thickness, it is possible to suppress the change in the transmittance of the wavelength band extending from the 匕 line to the g line to 1.5% or less. 2) Compared with the case of using a CrN single-layer film (Previous Example 2), it is easy to adjust and control to a desired transmittance, and it is particularly easy to finely adjust the transmittance. 3) A process of forming a semi-transmissive film first can be used; 4) Compared with the case of using a MoSiN single-layer film (previous example), the MoSiN film can be thinned, so that the etching time can be shortened. Specifically, the film thickness was about 丨/3 as compared with the previous example 1, and the appropriate etching time was about 丨/5. 5) Compared with the MoSi single-layer film (Hebei 8丨, M〇sm, etc.), the sheet resistance is low in the state of the laminated film. It is generally considered that although the 5^〇8 lanthanide film is non-conductive, it can be electrically conductive by the piercing effect of the CrN film in contact with the lower layer. 143513.doc -18- 201017328. 6) It is excellent in light resistance and chemical resistance as compared with a MoSi single layer film (MoSi, MoSiN, etc.). Since the CrN film is excellent in light resistance and chemical resistance, the semi-transmissive film containing the laminated film is also excellent in light resistance and chemical resistance. - 7) layers in a laminated structure in which a semi-transmissive CrN film (lower layer), a semi-transmissive MoSi film (upper layer) in contact therewith, and a core-shielding film in contact therewith are laminated from the substrate side Between, a higher etching selectivity ratio can be obtained. In the reticle base and the reticle of the present invention, the semi-transmissive film including the laminated film may have a two-layer structure (two-layer film), or may have a multilayer structure (multilayer film) of three or more layers. In the present invention, each of the semi-transmissive films constituting the laminated film may be a film containing a metal. In the present invention, the semi-transmissive film including the laminated film is preferably in the state of a laminated film, that is, the electric resistance is a sheet resistance value of kn/under. φ In the reticle base and the reticle of the present invention, as the material of the semi-transmissive film, it is preferable to select a thickness so that the transmittance of the light-transmitting portion is set to 1%%. Examples of the semi-transparent properties of about 60% (40 to 60%) include MoSi-based materials, Cr compounds (such as oxides, nitrides, nitrogen oxides, and fluorides), Si, and W. A1 and so on. Si, W, A1, etc., because of their film thickness, can obtain a material having a high light-shielding property or a semi-transmissive property. Here, the material of the semi-transmissive medium is not limited to the MoSi-based material composed of Mo and Si. The metal and ruthenium (MSi, wherein lanthanide M〇, Ta, W, 143513.doc -19- 201017328) are exemplified.
Ni、Zr、Ti、Cr等之過渡金屬）、經氧化氮化之金屬及矽 (MSiON)、經氧化碳化之金屬及矽（MSi(：〇)、經氧化氮化 碳化之金屬及石夕（MSiCON)、經氧化之金屬及石夕（Msi〇)、 以及經氮化之金屬及矽（MSiN)等。 本發明之光罩基底及光罩中’遮光膜之材質宜為藉由選 擇膜厚而可獲得高遮光性者，可列舉例如Cr、、w、 等。 作為遮光膜之材質，可列舉例如CrN、CrO、、 CrON等將Cr作為主成分者。遮光膜可為該等之單層，亦 可為將該等加以積層而成者。遮光膜宜為於包含Cr之遮光 層上積層有包含Cr化合物（CrO、CrN、或CrC)之抗反射層 者。 本發明之多色調光罩中，如圖9(1)中之一例所示，含有 如下態樣，即使上述半透光部係於透光性基板2丨上，形成 有僅由積層有2個半透光膜22、23之構造之半透光膜所構 成的半透光部（構成6)。 本發明之多色調光罩中，如圖9(2)中之一例所示，含有 如下態樣，即，上述半透光部具有曝光之光的透射率不同 之第1半透光部與第2半透光部，上述第丨半透光部係於透 光性基板21上，形成有僅由上述積層構造之半透光膜之下 層膜22所構成之半透光部，上述第2半透光部係於透光性 基板21上，形成有由上述積層構造之半透光膜之下層膜u 及上層膜23之積層膜所構成的半透光部（構成7)。於該情形 時，使用具有固定透射率之半透光膜作為上層之半透光膜 143513.doc 201017328 23 ’選擇性地保留上層之半透光膜23，藉此可獲得4色調 光罩。 本發明中’當將透光性基板之露出之透光部的曝光之光 之透射率設為100%之情形，半透光膜之曝光之光的透射 率以20〜60%為佳，更佳為4〇〜6〇%。此處，所謂透射率係 指相對於使用多色調光罩之例如大型Lcd用曝光機之曝光 之光的波長之透射率。 ^ 本發明中’當所形成之光罩之遮光部係由半透光膜及遮 光膜積層而成之情形’即便遮光膜單獨之遮光性不足，只 要與半透光膜組合之後可獲得遮光性即可。 本發明中’理想的是’當自基板側起，半透光膜之下 層、與其接觸之半透光膜之上層、以及與其接觸之遮光膜 成膜於基板上時，相互間之密著性良好。 本發明中，具有於透光性基板上形成半透光膜、遮光膜 之步驟’但成膜方法可適當地選擇適合於膜之類型之方 ❹ 法例如，賤鐘法、蒸鑛法、CVD(Chemical Vapor Deposition， 化學氣相沈積）法等。 本發明中’作為包含含有金屬及矽之材料之半透光膜之 . 钮刻液可使用含有選自氫氟酸、妙氫氟酸、氫氟錄中之 至少一種氟化合物、以及選自過氧化氫、硝酸、硫酸中之 至少一種氧化劑的蝕刻液。 本發明中，作為含有Cr之材料之蝕刻液，可使用含有硝 酸鈽銨之蝕刻液。 本發月之多色調光罩係TFT(Thin Film Transistor，薄膜 143513.doc -21- 201017328 電晶體）製造用之多色調光罩及光罩基底，半透光部可較 好地用作對相當於該薄膜電晶體之通道部之部分的圖案進 行轉印者。 圖η中表示TFT基板製造用之光罩圖案之一例。tft基 板製造用之圖案100包括：遮光部101，其包含與tft基板 之源極及汲極相對應之圖案101a、101b ;半透光部1〇3， 其包含與TFT基板之通道部相對應之圖案；以及透光部 102’其形成於上述圖案之周圍。 本發明之圖案轉印方法可較好地用作包含如下步驟之圖 案轉印方法，於該步驟中’使用上述構成5至7中任一項之 光罩’且藉由遍及i線〜g線之波長帶的曝光之光，而將形 成於光罩之多色調圖案轉印至被轉印體（構成8)。 本發明中’作為遍及i線~g線之波長帶的曝光之光源， 例示有超高壓水銀燈等，但本發明並不限定於此。 以下’基於實施例對本發明進行更詳細之說明。 (實施例1) (光罩基底之製作） 準備由各種半透光膜分別以單層、積層之形式而形成於 基板上所得之試樣（下述（1)~(3))。 (1) CrN膜 使用Cr靶，將Ar與NJ8 : 2 seem)氣體作為濺鍍氣體，將 CrN膜（半透光膜）以相對於曝光之光源之波長之透射率為 40%的膜厚（約88埃）而成膜於基板上。 圖1(1)表示所獲得之CrN膜之、i線（365 nm)、h線（405 143513.doc • 22· 201017328 nm)、g線（43 6 nm)的透射率（°/〇)、反射率（°/〇)、i線〜g線之波 長帶上之透射率、反射率的最大值與最小值之差。又，圖 1(2)表示所獲得之CrN膜之膜厚及薄片電阻（kQ/c:)。進而， 所獲得之CrN膜之透射率光譜表示於圖2中，相對反射率光 譜表示於圖3中。 (2) MoSiN膜 使用Mo:Si=20:80(原子百分比）之靶，將Ar與N2作為濺鍍 氣體（流量比為Ar 5 :N2 50 seem)，將包含翻及石夕之氮化膜 之半透光膜（MoSiN膜）分別以約120埃之膜厚、及約330埃 之膜厚而形成於基板上。 將所獲得之MoSiN膜中之膜厚較薄者記作MoSiN-Ι，將 膜厚較厚者記作MoSiN-2。 圖 1(1)表示所獲得之MoSiN膜（MoSiN-Ι、MoSiN-2)之、i 線（3 65 nm)、h線（405 nm)、g線（43 6 nm)之透射率（％)、反 射率（％)、i線〜g線之波長帶上之透射率、反射率的最大值 與最小值之差。又，圖1(2)表示所獲得之MoSiN膜（MoSiN-1、MoSiN-2)之膜厚及薄片電阻（kD/[=i)。進而，圖2表示所 獲得之MoSiN膜（MoSiN-Ι、MoSiN-2)之透射率光譜，圖3 表示相對反射率光譜。 (3) 積層膜 將於基板上依序形成有與上述相同之CrN膜、膜厚較薄 之 MoSiN 膜（MoSiN-Ι)的試樣記作 CrN+MoSiN-Ι。 將於基板上依序形成有與上述相同之CrN膜、膜厚較厚 之MoSiN膜（MoSiN-2)的試樣記作 CrN+MoSiN-2。 143513.doc -23- 201017328 圖1(1)表示所獲得之試樣（CrN+MoSiN-l、CrN+MoSiN-2)之、i線（365 nm)、h線（405 nm)、g線（436 nm)之透射率 (%)、反射率（％)、i線〜g線之波長帶上之透射率、反射率 的最大值與最小值之差。又，圖1(2)表示所獲得之試樣 (CrN+MoSiN-l 、 CrN+MoSiN-2)之膜厚及薄片電阻 (kQ/iD)。進而，圖2表示所獲得之試樣（CrN+MoSiN-l、 CrN+MoSiN-2)之透射率光譜，圖3表示相對反射率光譜。 再者，於上述成膜步驟中，使用有大型玻璃基板（厚度 為10 mm、尺寸為850 mmx 1200 .mm之合成石英（QZ))，且 使用有大型連續式濺鍍裝置。 又，圖1(1)及圖3中之「相對反射率」表示以鋁（A1)之反 射率為基準（100%)而測定之反射率。 (評價） 關於CrN/MoSiN之積層膜，當MoSiN之膜厚恰當之情形 (於CrN+MoSiN-l之試樣之情形之情形），可獲得將遍及i 線〜g線之波長帶之透射率變化量抑制為1.5%以下的效果。 又，可利用MoSiN之膜厚而對透射率進行微調整。相對於 此，當MoSiN之膜厚不恰當（於CrN+MoSiN-2之試樣之情形 時），無法獲得抑制遍及i線〜g線之波長帶之透射率變化量 的效果。 (實施例2) (光罩基底之製作） 準備由各種半透光膜分別以單層、積層之形式而形成於 基板上所得之試樣。 143513.doc -24- 201017328 (1) CrN膜 使用Cr靶，將心與乂（8:2 sccm)氣體作為濺鍍氣體，將 CrN膜（半it光膜）以相對於曝光之光源之波長的透射率為 40%之膜厚（約78埃）而成膜於基板上。 ； 圖4(1)表示所獲得之CrN膜之、i線（365 nm)、^線^… nm)、g線（436 nm)之透射率（％)、反射率（％)、丨線〜g線之波 長帶上之透射率、反射率的最大值與最小值之差。又，圖 4(2)表示所獲得之CrN膜之膜厚及薄片電阻（kfi/口）。進而， 圖5表示所獲得之CrN膜之透射率光譜，圖6表示相對反射 率光譜。 (2) MoSi膜 使用Mo:Si=20:80(原子百分比）之靶，將Ar作為濺鍍氣 體，將包含鉬及石夕之半透光膜（M〇Si膜）以約22〇埃之膜厚 而形成於基板上。 圖4(1)表示所獲得2M〇Si膜之、匕線（365 nm)、11線（4〇5 參 nm)、g線（436 nm)之透射率（％)、反射率（％)、丨線〜g線之波 長帶上之透射率、反射率的最大值與最小值之差。又，圖 4(2)表示所獲得之MOSi膜之膜厚及薄片電阻（ki2/[：)。進 而，圖5表示所獲得之]^〇8丨膜之透射率光譜，圖6表示相對 反射率光譜。 (3) 積層膜 將基板上依序形成有與上述相同之CrN膜、MoSi膜之試 樣記作CrN+MoSi。 圖4(1)表示所獲得之試樣（CrN+M〇Si)之、丨線（365 nm)、 143513.doc -25- 201017328 h線（405 nm)、g線（43 6 nm)之透射率（％)、反射率（％)、} 線〜g線之波長帶上之透射率、反射率的最大值與最小值之 差。又，圖4(2)表示所獲得之試樣（CrN+M〇Si)之膜厚及薄 片電阻（kQ/ci)。進而，圖5表示所獲得之試樣（CrN+M〇Si) 之透射率光譜’圖6表示相對反射率光譜。 再者，於上述成膜步驟中，使用有大型玻璃基板（厚度 為10 mm、尺寸為85 0 mmxl200 mm之合成石英（QZ))，且 使用有大型連續式濺鍍裝置。 又，圖4(1)及圖6中之「相對反射率」係表示以鋁（A1)之 反射率為基準（100%)而測定之反射率。 (評價） 若利用「i線-g線間之透射率變動相對較小，且用以獲得 特疋之透射率之膜厚相對較厚，因此易於對透射率進行調 整、控制」之CrN膜、與「i線_g線間之透射率變動相對較 小，但用以獲得特定之透射率之膜厚相對較薄，因此難以 對透射率進行調整、控制」iM〇Si膜之積層膜而構成半透 光膜，則可獲得將遍及i線〜g線之波長帶之透射率變化量 抑制為2.0%以下的效果。 於實施例2中，可利用CrN膜、MoSi膜中之任一方之膜 或雙方之膜之膜厚而調整透射率。又，根據％〇以膜之成膜 條件而調整MoSi膜之透射率，藉此，亦可調整包含積層膜 之半透光膜之透射率。進而，可利fflM〇SiN之臈厚而對透 射率進行微調整。 (實施例3) 143513.doc -26- 201017328 (光罩基底之製作） 於大型玻璃基板（厚度為10 mm、尺寸為85〇 mmxl2〇〇 mm之合成石英（QZ))上，利用大型連續式濺鍍裝置而形成 多色調光罩用之半透光膜。具體而言，使用心靶，將^與 Ν2(8··2 SCCm)氣體作為濺鍍氣體，以相對於曝光之光源之 波長之透射率為40%的膜厚（約88埃）而形成crN膜（半透光 . 膜）。 參 繼而’於上述半透光膜上，使用Mo:Si=20:80(原子百分 比）之輕’將Ar與&作為濺鍍氣體（流量比為Ar 5:n2 5〇 seem)，以約120埃之膜厚而形成包含鉬及矽之氮化膜之半 透光膜之上層膜（MoSiN)。 積層有半透光膜之下層膜（CrN)與半透光膜之上層膜 (MoSiN)之狀態下之積層膜之薄片電阻係呈現i 口以下 之導電性。 繼而，於上述半透光膜之上層膜上，作為遮光膜，首 ❹ 先’將^與乂氣體作為濺鍍氣體而形成150埃之CrN媒， 繼而，將Ar與CH4氣體作為濺鍍氣體而形成65〇埃之CrC膜 (主遮光膜），其後，將八!*與NO氣體作為濺鍍氣體而形成 250埃之CrON膜（膜面抗反射膜），以此方式連續成膜。再 者’各膜分別係組成傾斜膜。 以上述方式，製作FPD用大型光罩基底。 (多色調光罩之製作） 準備如下之光罩基底（參照圖8(1))，該光罩基底中，參 照圖7，以上述方式而於透光性基板21(QZ)上依序形成有 143513.doc -27- 201017328 包含半透光膜22(CrN)與半透光膜23(M〇SiN)之積層膜的半 透光膜24、以及遮光膜30(自基板側起為CrN膜31/CrC遮光 膜32/CrON抗反射膜33)。 繼而，於該光罩基底上，例如利用CAp塗佈裝置而塗佈 電子束或雷射描繪用之正型光阻劑，且將其進行烘乾，從 而形成光阻膜《其次，使用電子束描繪機或雷射描繪機等 而進行描繪。於描繪之後使其顯影，於光罩基底上之除透 光部以外之區域（亦即與遮光部及半透光部相對應之區域） 中形成光阻圖案50a(參照圖8(2))。 繼而，將所形成之光阻圖案5〇3作為光罩，對遮光膜3〇 進行濕式蝕刻而形成遮光膜圖案3〇a(參照圖8(3))。所使用 之飯刻液係於靖酸鈽錢中添加有過氣酸者。 繼而，於除去光阻圖案50a之後’將遮光膜圖案3〇a作為 光罩，對上層之半透光膜23(MoSiN)進行濕式蝕刻，從而 形成半透光膜（MoSiN)之圖案23a(參照圖8(4))。所使用之 姓刻液係於氫氟錢中添加有過氧化氫者。 繼而，將遮光膜圖案30a作為光罩，對下層之半透光膜 22(CrN)進行濕式蝕刻，從而形成半透光膜之圖案 22a(參照圖8(5))。所使用之姓刻液係於確酸飾銨中添加有 過氣酸者。 繼而，再次將上述光阻劑塗佈於整個面上而形成光阻 臈。接著，進行第2次描繪。於描繪之後使其顯影，形成 與遮光部及透光部相對應之光阻圖案51a(參照圖8(6))。 繼而，將所形成之光阻圖案51a作為光罩，利用漁式蝕 143513.doc 201017328 刻而除去成為半透光部之區域之遮光臈圖案3〇a。藉此， 除去半透光部上之透光膜，並且形成遮光臈圖案3〇b(參照 圖 8(7))。 最後，利用濃硫酸等而除去殘存之光阻圖案5丨a(參照圖 8(8)) 〇 以上述方式製成多色調光罩。 (評價） 根據上述實施例3之發明，確認可提供一種可同時滿足 _ 下述（1)〜(3)之FPD用大型多色調光罩基底及光罩、以及其 等之製造方法。 (1) 抑制半透光膜之遍及i線〜g線之波長帶的透射率變化 量； (2) 將透過半透光膜的曝光之光的透射率調整為所期望之值 (尤其是容易進行微調整）； (3) 可採用缺陷少之製程。 (實施例4) 繼上述實施例3中之圖8之步驟（8)之後，對於包含下層 之半透光膜（CrN)圖案22a與上層之半透光膜（MoSiN)圖案 23 a之積層膜的半透光膜圖案24a之一部分，形成新的光阻 圖案而進行保護。其後，利用蝕刻液（於氫氟銨中添加有 過氧化氫者）’對不受光阻圖案保護之半透光膜圖案2牝之 上層的半透光膜（MoSiN)圖案23a進行蝕刻，形成僅包含下 層之半透光膜（CrN)圖案22a之半透光部。 除去光阻圖案24a，製成如下之多色調（4色調）光罩，該 143513.doc -29· 201017328 多色調（4色調）光罩具有包含下層之半透光膜（CrN)圖案22a 與上層之半透光膜（MoSiN)圖案23a之積層膜的半透光部、 僅包含下層之半透光膜（CrN)圖案22a之半透光部、遮光 部、以及透光部（參照圖9(2))。 評價結果與實施例3相同。 以上’以較佳實施例對本發明進行了說明，但本發明並 不限定於上述實施例。 【圖式簡單說明】 圖1 (1 )、圖1 (2)係表示本發明之實施例i中所得之各種半 © 透光臈的光學特性等之圖； 圖2係表示本發明之實施例1中所得之各種半透光膜的透 射率光譜之圖； 圖3係表示本發明之實施例1中所得之各種半透光膜的反 射率光譜之圖； 圖4(1)、圖4(2)係表示本發明之實施例2中所得之各種半 透光臈的光學特性等之圖； 圖5係表示本發明之實施例2中所得之各種半透光膜的透 射率光譜之圖； 圖6係表示本發明之實施例2中所得之各種半透光膜的反 射率光譜之圖； 圖7係表示本發明之實施例3中製作之光罩基底之模式性 剖面圖； 圖80)〜圖8(8)係按照步驟而表示本發明之實施例3之製 造方法的概略剖面圖； 1435l3.doc •30- 201017328 圖9⑴、圖9(2)係用以說明半透光部之態樣之模式圖； 圖10(1)、圖1G⑺係用以說明半透光膜與遮光膜之成膜 順序之差異的圖’圖1〇⑴表示先形成半透光膜之類型之光 罩，圖10(2)表示後形成半透光膜之類型之光罩； 圖11(1)、圖11(2)係用以說明具有半透光膜之多色調光 罩之圖’㈣⑴係局部平面圖，圖11(2)係局部剖面圖； 圖12( 1 )、圖12(2)係用以說明具有解像極限以下之微細 遮光圖案之多色調光罩之圖’圖12(1)係局部平面圖，圖 12 ( 2 )係局部剖面圖；及 圖13係表示TFT基板製造用之光罩圖案之一例的圖。 【主要元件符號說明】 1、ιοί 遮光部 1' 與遮光部1相對應之部分 2、102 透光部 V 與透光部2相對應之部分 3、103 半透光部 3' 與半透光部3相對應之部分 3a 微細遮光圖案 3b 微細透射部 3a'、22、23、24 半透光膜 5、21 光性基板 22a 半透光膜（CrN)圖案 23a 半透光膜（MoSiN)圖案 24a 半透光膜圖案 143513.doc 201017328 30 遮光膜 30a、30b 遮光膜圖案 31 CrN膜 32 CrC遮光膜 33 CrON抗反射膜 50a ' 51a 光阻圖案 100 TFT基板製造用之圖案 101a、101b 圖案 143513.doc -32-Transition metals such as Ni, Zr, Ti, Cr, etc., oxidized and nitrided metals and cerium (MSiON), oxidized carbonized metals and cerium (MSi (: 〇), carbonized by oxidized nitriding and Shi Xi ( MSiCON), oxidized metal and shovel (Msi〇), and nitrided metal and yttrium (MSiN), etc. The material of the opaque film and the reticle of the present invention is preferably selected by film thickness For the light-shielding film, for example, Cr, CrO, or CrON may be used as the main component. The light-shielding film may be such a single layer. It is also possible to laminate the layers. The light-shielding film is preferably an anti-reflection layer containing a Cr compound (CrO, CrN, or CrC) laminated on a light-shielding layer containing Cr. The multi-tone mask of the present invention As shown in an example of Fig. 9 (1), the semi-transmissive portion is formed on the light-transmitting substrate 2, and only two semi-transmissive films 22, 23 are formed by lamination. A semi-transmissive portion (constitution 6) composed of a semi-transmissive film of the structure. In the multi-tone mask of the present invention, as shown in FIG. 9 (2) In the example, the semi-transmissive portion has a first semi-transmissive portion and a second semi-transmissive portion having different transmittances of exposed light, and the first semi-transmissive portion is permeable to light. The semi-transmissive portion formed of the semi-transmissive film underlayer film 22 of the laminated structure is formed on the substrate 21, and the second semi-transmissive portion is formed on the translucent substrate 21, and the laminated layer is formed. a semi-transmissive portion (constitution 7) formed by a laminated film of the underlying film u and the upper film 23 of the semi-transmissive film. In this case, a semi-transmissive film having a fixed transmittance is used as the semi-transparent layer of the upper layer. Film 143513.doc 201017328 23 'Selectively retains the upper semi-transmissive film 23, whereby a 4-tone mask can be obtained. In the present invention, the transmission of the exposed light of the light-transmitting portion of the light-transmitting substrate is transmitted. When the ratio is set to 100%, the transmittance of the light of the semi-transmissive film is preferably 20 to 60%, more preferably 4 to 6 %. Here, the transmittance means relative to the use of multi-tone. The transmittance of the wavelength of the light of the exposure of the exposure lens such as the large Lcd. ^ In the present invention The light-shielding portion of the photomask is formed by laminating a semi-transmissive film and a light-shielding film. Even if the light-shielding film alone has insufficient light-shielding properties, it is only required to be combined with the semi-transmissive film to obtain light-shielding properties. In the present invention, when the lower layer of the semi-transmissive film, the upper layer of the semi-transmissive film in contact therewith, and the light-shielding film in contact therewith are formed on the substrate from the substrate side, the adhesion therebetween is good. There is a step of forming a semi-transparent film and a light-shielding film on a light-transmitting substrate. However, the film forming method can appropriately select a method suitable for the type of the film, for example, a chirp method, a steaming method, or a CVD (Chemical Vapor). Deposition, chemical vapor deposition), etc. In the present invention, 'as a semi-transmissive film containing a material containing a metal and a ruthenium. The button engraving liquid may use at least one fluorine compound selected from the group consisting of hydrofluoric acid, dihydrohydrofluoric acid, and hydrofluorocarbon, and is selected from the group consisting of An etching solution of at least one of oxidizing agents such as hydrogen peroxide, nitric acid, and sulfuric acid. In the present invention, as the etching liquid of the material containing Cr, an etching solution containing ammonium cerium nitrate can be used. The polychromatic mask of the present month is a multi-tone mask and a reticle substrate for manufacturing a TFT (Thin Film Transistor, film 143513.doc -21 - 201017328 transistor), and the semi-transmissive portion can be preferably used as a pair equivalent The pattern of the portion of the channel portion of the thin film transistor is transferred. An example of a mask pattern for manufacturing a TFT substrate is shown in FIG. The pattern 100 for manufacturing a tft substrate includes a light shielding portion 101 including patterns 101a and 101b corresponding to the source and the drain of the tft substrate, and a semi-transmissive portion 1〇3 including the channel portion of the TFT substrate. a pattern; and a light transmitting portion 102' formed around the pattern. The pattern transfer method of the present invention can be preferably used as a pattern transfer method comprising the steps of 'using the photomasks of any of the above-mentioned configurations 5 to 7' and by passing through the i-line to the g-line The multi-tone pattern formed in the photomask is transferred to the object to be transferred (constitution 8) by the exposure light of the wavelength band. In the present invention, an ultrahigh pressure mercury lamp or the like is exemplified as a light source for exposure in a wavelength band of the i-th to g-line, but the present invention is not limited thereto. The present invention will now be described in more detail based on the examples. (Example 1) (Production of Photomask Base) A sample obtained by forming a plurality of semi-transmissive films on a substrate in the form of a single layer or a laminate was prepared (the following (1) to (3)). (1) The CrN film uses a Cr target, and Ar and NJ8: 2 seem) gases are used as a sputtering gas, and the CrN film (semi-transmissive film) has a film thickness of 40% with respect to the wavelength of the light source to be exposed ( About 88 angstroms) was formed on the substrate. Figure 1 (1) shows the transmittance (°/〇) of the obtained CrN film, i-line (365 nm), h-line (405 143513.doc • 22·201017328 nm), g-line (43 6 nm), The reflectance (°/〇), the transmittance on the wavelength band of the i-line to the g-line, and the difference between the maximum value and the minimum value of the reflectance. Further, Fig. 1 (2) shows the film thickness and sheet resistance (kQ/c:) of the obtained CrN film. Further, the transmittance spectrum of the obtained CrN film is shown in Fig. 2, and the relative reflectance spectrum is shown in Fig. 3. (2) The MoSiN film uses a target of Mo:Si=20:80 (atomic percent), and Ar and N2 are used as sputtering gases (flow ratio: Ar 5 : N 2 50 seem), which will include a nitride film of Turning and Shi Xi The semi-transmissive film (MoSiN film) is formed on the substrate by a film thickness of about 120 angstroms and a film thickness of about 330 angstroms. The film thickness of the obtained MoSiN film was referred to as MoSiN-Ι, and the film thickness was referred to as MoSiN-2. Fig. 1 (1) shows the transmittance (%) of the obtained MoSiN film (MoSiN-Ι, MoSiN-2), i-line (3 65 nm), h-line (405 nm), and g-line (43 6 nm). The reflectance (%), the transmittance on the wavelength band of the i-line to the g-line, and the difference between the maximum value and the minimum value of the reflectance. Further, Fig. 1 (2) shows the film thickness and sheet resistance (kD / [= i) of the obtained MoSiN film (MoSiN-1, MoSiN-2). Further, Fig. 2 shows the transmittance spectrum of the obtained MoSiN film (MoSiN-Ι, MoSiN-2), and Fig. 3 shows the relative reflectance spectrum. (3) Laminated film A sample in which a CrN film having the same thickness as above and a MoSiN film (MoSiN-Ι) having a small film thickness were sequentially formed on the substrate was referred to as CrN+MoSiN-Ι. A sample in which a CrN film having the same thickness as above and a MoSiN film (MoSiN-2) having a relatively large thickness were sequentially formed on the substrate was designated as CrN + MoSiN-2. 143513.doc -23- 201017328 Figure 1 (1) shows the obtained sample (CrN+MoSiN-1, CrN+MoSiN-2), i-line (365 nm), h-line (405 nm), g-line ( The transmittance (%) of 436 nm), the reflectance (%), the transmittance on the wavelength band of the i-line to the g-line, and the difference between the maximum value and the minimum value of the reflectance. Further, Fig. 1 (2) shows the film thickness and sheet resistance (kQ/iD) of the obtained samples (CrN + MoSiN-1, CrN + MoSiN-2). Further, Fig. 2 shows the transmittance spectra of the obtained samples (CrN + MoSiN-1, CrN + MoSiN-2), and Fig. 3 shows the relative reflectance spectra. Further, in the above film forming step, a large glass substrate (synthetic quartz (QZ) having a thickness of 10 mm and a size of 850 mm x 1200 mm) was used, and a large continuous sputtering apparatus was used. Further, the "relative reflectance" in Fig. 1 (1) and Fig. 3 indicates the reflectance measured based on the reflectance of aluminum (A1) (100%). (Evaluation) Regarding the laminated film of CrN/MoSiN, when the film thickness of MoSiN is appropriate (in the case of the sample of CrN+MoSiN-1), the transmittance of the wavelength band across the i-line to the g-line can be obtained. The amount of change is suppressed to 1.5% or less. Further, the transmittance can be finely adjusted by using the film thickness of MoSiN. On the other hand, when the film thickness of MoSiN is not appropriate (in the case of a sample of CrN + MoSiN-2), the effect of suppressing the amount of change in transmittance in the wavelength band of the i line to the g line cannot be obtained. (Example 2) (Production of Photomask Base) A sample obtained by forming various semi-transmissive films on a substrate in the form of a single layer or a laminate was prepared. 143513.doc -24- 201017328 (1) The CrN film uses a Cr target, a heart and helium (8:2 sccm) gas as a sputtering gas, and a CrN film (half-it light film) at a wavelength relative to the source of the exposure light. A film thickness (about 78 angstroms) having a transmittance of 40% was formed on the substrate. Fig. 4(1) shows the transmittance (%), reflectance (%), and 丨 line of the obtained CrN film, i-line (365 nm), ^ line ^... nm), g-line (436 nm). The difference between the maximum and minimum values of the transmittance and reflectance in the wavelength band of the g-line. Further, Fig. 4 (2) shows the film thickness and sheet resistance (kfi / port) of the obtained CrN film. Further, Fig. 5 shows the transmittance spectrum of the obtained CrN film, and Fig. 6 shows the relative reflectance spectrum. (2) The MoSi film uses a target of Mo:Si=20:80 (atomic percent), and Ar is used as a sputtering gas, and a semi-transmissive film (M〇Si film) containing molybdenum and a stone is placed at about 22 Å. The film thickness is formed on the substrate. 4(1) shows the transmittance (%), reflectance (%), and the reflectance (%) of the obtained 2M 〇Si film, 匕 line (365 nm), 11 line (4〇5 参 nm), g line (436 nm), The difference between the maximum and minimum values of the transmittance and reflectance in the wavelength band of the 丨 line to the g line. Further, Fig. 4 (2) shows the film thickness and sheet resistance (ki2 / [:) of the obtained MOSi film. Further, Fig. 5 shows the transmittance spectrum of the obtained film, and Fig. 6 shows the relative reflectance spectrum. (3) Laminated film A sample in which a CrN film or a MoSi film similar to the above was sequentially formed on the substrate was designated as CrN + MoSi. Figure 4(1) shows the transmission of the obtained sample (CrN+M〇Si), the 丨 line (365 nm), the 143513.doc -25-201017328 h line (405 nm), and the g line (43 6 nm). Rate (%), reflectance (%), and the difference between the maximum and minimum values of the transmittance and the reflectance in the wavelength band of the line to the g line. Further, Fig. 4 (2) shows the film thickness and sheet resistance (kQ/ci) of the obtained sample (CrN + M 〇 Si). Further, Fig. 5 shows a transmittance spectrum of the obtained sample (CrN + M 〇 Si). Fig. 6 shows a relative reflectance spectrum. Further, in the above film forming step, a large glass substrate (synthetic quartz (QZ) having a thickness of 10 mm and a size of 85 0 mm x 200 mm) was used, and a large continuous sputtering apparatus was used. Further, the "relative reflectance" in Fig. 4 (1) and Fig. 6 indicates the reflectance measured based on the reflectance of aluminum (A1) (100%). (Evaluation) The CrN film which is easy to adjust and control the transmittance by using a relatively small transmittance change between the i-line and the g line and having a relatively large transmittance to obtain a transmittance of the characteristic is used. The transmittance variation between the "i line and the g line is relatively small, but the film thickness for obtaining a specific transmittance is relatively small. Therefore, it is difficult to adjust the transmittance and control the laminated film of the iM〇Si film. In the semi-transmissive film, the effect of suppressing the change in transmittance in the wavelength band of the i-line to the g-line to 2.0% or less can be obtained. In the second embodiment, the transmittance can be adjusted by using the film thickness of either or both of the CrN film and the MoSi film. Further, the transmittance of the MoSi film can be adjusted according to the film formation conditions of the film, whereby the transmittance of the semi-transmissive film including the laminate film can be adjusted. Further, it is possible to finely adjust the transmittance by making the thickness of fflM〇SiN thick. (Example 3) 143513.doc -26- 201017328 (Production of reticle base) On a large glass substrate (synthesis quartz (QZ) having a thickness of 10 mm and a size of 85 〇 mm x 12 mm), a large continuous type was used. A semi-transmissive film for a multi-tone mask is formed by a sputtering apparatus. Specifically, using a cardiac target, a gas of ^2 and Ν2 (8·2 SCCm) is used as a sputtering gas to form a crN with a film thickness (about 88 angstroms) of a transmittance of 40% with respect to the wavelength of the light source to be exposed. Membrane (semi-transparent. Membrane). Then, on the semi-transmissive film, using Ar:Mo:Si=20:80 (atomic percent) light, Ar and & as a sputtering gas (flow ratio: Ar 5:n2 5〇seem), A film of 120 angstroms thick forms a semi-transmissive film overlayer film (MoSiN) containing a nitride film of molybdenum and niobium. The sheet resistance of the laminated film in the state in which the semi-transmissive film underlayer film (CrN) and the semi-transmissive film overlayer film (MoSiN) are laminated exhibits conductivity of i or less. Then, on the overlying film of the semi-transmissive film, as a light-shielding film, first, a gas is used as a sputtering gas to form a 150 Å CrN medium, and then Ar and CH4 gases are used as a sputtering gas. A CrC film (main light-shielding film) of 65 angstroms was formed, and thereafter, a CrON film (film surface anti-reflection film) of 250 angstroms was formed by using Ba** and NO gas as a sputtering gas, and film formation was continuously performed in this manner. Further, each of the films constitutes a slanted film. In the above manner, a large reticle base for FPD was produced. (Production of Multi-Color Mask) The following mask base is prepared (see Fig. 8 (1)), and the mask base is sequentially formed on the light-transmitting substrate 21 (QZ) in the above-described manner with reference to Fig. 7 There is a semi-transmissive film 24 including a laminated film of a semi-transmissive film 22 (CrN) and a semi-transmissive film 23 (M〇SiN), and a light shielding film 30 (a CrN film from the substrate side) 143513.doc -27- 201017328 31/CrC light-shielding film 32/CrON anti-reflection film 33). Then, on the reticle substrate, an electron beam or a positive photoresist for laser drawing is applied, for example, by a CAp coating device, and dried to form a photoresist film. Second, an electron beam is used. Drawing is performed by a drawing machine, a laser drawing machine, or the like. After the drawing, the photoresist pattern 50a is formed in a region other than the light transmitting portion (that is, a region corresponding to the light shielding portion and the semi-light transmitting portion) on the mask substrate (refer to FIG. 8 (2)). . Then, the formed photoresist pattern 5〇3 is used as a photomask, and the light-shielding film 3〇 is wet-etched to form a light-shielding film pattern 3〇a (see Fig. 8(3)). The rice broth used is one in which sulphuric acid is added to the sulphuric acid. Then, after the photoresist pattern 50a is removed, the light-shielding film pattern 3〇a is used as a mask, and the upper semi-transmissive film 23 (MoSiN) is wet-etched to form a semi-transmissive film (MoSiN) pattern 23a ( Refer to Figure 8(4)). The surname used is the one in which hydrogen peroxide is added to the hydrofluorocarbon. Then, the light-shielding film pattern 30a is used as a mask, and the lower semi-transmissive film 22 (CrN) is wet-etched to form a semi-transmissive film pattern 22a (see Fig. 8 (5)). The surname used is the one in which the acid is added to the acid. Then, the above photoresist is applied again over the entire surface to form a photoresist. Next, the second drawing is performed. After the drawing, the film is developed to form a photoresist pattern 51a corresponding to the light shielding portion and the light transmitting portion (see Fig. 8 (6)). Then, the formed photoresist pattern 51a is used as a mask, and the light-shielding pattern 3〇a which is a region of the semi-light-transmitting portion is removed by the fishing etching 143513.doc 201017328. Thereby, the light-transmissive film on the semi-transmissive portion is removed, and the light-shielding pattern 3〇b is formed (refer to Fig. 8 (7)). Finally, the remaining photoresist pattern 5丨a is removed by using concentrated sulfuric acid or the like (see Fig. 8 (8)). 多 A multi-tone mask is produced in the above manner. (Evaluation) According to the invention of the third embodiment, it is confirmed that a large-sized multi-tone mask base and a photomask for FPD which can simultaneously satisfy the following (1) to (3), and a method of manufacturing the same can be provided. (1) suppressing the amount of change in transmittance of the semi-transmissive film across the wavelength band of the i-line to the g-line; (2) adjusting the transmittance of the light that has passed through the semi-transmissive film to a desired value (especially easy Make minor adjustments); (3) Processes with few defects can be used. (Embodiment 4) Subsequent to the step (8) of Fig. 8 in the above-mentioned Embodiment 3, a laminated film comprising the underlying semi-transmissive film (CrN) pattern 22a and the upper semi-transmissive film (MoSiN) pattern 23a A portion of the semi-transmissive film pattern 24a is formed by forming a new photoresist pattern. Thereafter, the semi-transmissive film (MoSiN) pattern 23a of the upper layer of the semi-transmissive film pattern 2牝 not protected by the photoresist pattern is etched by using an etching solution (addition of hydrogen peroxide to the hydrofluoroammonium). Only the semi-transmissive portion of the lower semi-transmissive film (CrN) pattern 22a is included. The photoresist pattern 24a is removed to produce a multi-tone (4-tone) mask having a semi-transmissive film (CrN) pattern 22a and a lower layer including a lower layer as follows: 143513.doc -29·201017328 The semi-transmissive portion of the laminated film of the semi-transmissive film (MoSiN) pattern 23a, the semi-transmissive portion including only the lower semi-transmissive film (CrN) pattern 22a, the light shielding portion, and the light transmitting portion (refer to FIG. 9 (refer to FIG. 9 ( 2)). The evaluation results were the same as in Example 3. The present invention has been described above by way of preferred embodiments, but the present invention is not limited to the above embodiments. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 (1) and Fig. 1 (2) are views showing optical characteristics and the like of various semi-transparent iridium obtained in Example i of the present invention; Fig. 2 is a view showing an embodiment of the present invention. Fig. 3 is a view showing a reflectance spectrum of various semi-transmissive films obtained in Example 1 of the present invention; Fig. 4 (1), Fig. 4 (Fig. 4 (1), Fig. 4 (Fig. 4 (1), Fig. 4 (Fig. 4 (1), Fig. 4 2) is a view showing optical characteristics and the like of various semi-transmissive iridium obtained in Example 2 of the present invention; and FIG. 5 is a view showing a transmittance spectrum of various semi-transparent films obtained in Example 2 of the present invention; 6 is a view showing a reflectance spectrum of various semi-transmissive films obtained in Example 2 of the present invention; and FIG. 7 is a schematic cross-sectional view showing a base of a photomask produced in Example 3 of the present invention; FIG. 80) 8(8) is a schematic cross-sectional view showing the manufacturing method of the third embodiment of the present invention in accordance with the steps; 1435l3.doc • 30- 201017328 Fig. 9(1) and Fig. 9(2) are for explaining the state of the semi-transmissive portion. Figure 10 (1), Figure 1G (7) is used to illustrate the difference between the film formation order of semi-transparent film and light-shielding film 'Figure 1 (1) indicates a photomask of a type in which a semi-transparent film is formed first, and FIG. 10 (2) shows a photomask of a type in which a semi-transparent film is formed; FIGS. 11(1) and 11(2) are for explaining semi-transparent The picture of the multi-tone mask of the light film is (4) (1) is a partial plan view, and Figure 11 (2) is a partial cross-sectional view; Figure 12 (1) and Figure 12 (2) are used to illustrate the fine light-shielding pattern having the resolution limit or less. FIG. 12(1) is a partial plan view, FIG. 12(2) is a partial cross-sectional view, and FIG. 13 is a view showing an example of a mask pattern for manufacturing a TFT substrate. [Description of main component symbols] 1. ιοί The portion of the light-shielding portion 1' corresponding to the light-shielding portion 2, the portion of the light-transmitting portion V corresponding to the light-transmitting portion 2, the portion 3, 103, the semi-transmissive portion 3' and the semi-transparent portion Part 3 corresponding to portion 3a fine light-shielding pattern 3b fine-transmissive portion 3a', 22, 23, 24 semi-transmissive film 5, 21 optical substrate 22a semi-transmissive film (CrN) pattern 23a semi-transmissive film (MoSiN) pattern 24a semi-transmissive film pattern 143513.doc 201017328 30 light-shielding film 30a, 30b light-shielding film pattern 31 CrN film 32 CrC light-shielding film 33 CrON anti-reflection film 50a '51a photoresist pattern 100 TFT substrate manufacturing pattern 101a, 101b pattern 143513. Doc -32-
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| JP2008247271A JP5121020B2 (en) | 2008-09-26 | 2008-09-26 | Multi-tone photomask, photomask blank, and pattern transfer method |
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| JP6891099B2 (en) * | 2017-01-16 | 2021-06-18 | Hoya株式会社 | A phase shift mask blank, a method for manufacturing a phase shift mask using the blank, and a method for manufacturing a display device. |
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| JP3262302B2 (en) * | 1993-04-09 | 2002-03-04 | 大日本印刷株式会社 | Phase shift photomask, blank for phase shift photomask, and method of manufacturing the same |
| KR0172790B1 (en) * | 1995-09-18 | 1999-03-20 | 김영환 | Phase shift mask and the fabricating method therefor |
| JP4054951B2 (en) * | 2001-08-06 | 2008-03-05 | 信越化学工業株式会社 | Method for manufacturing phase shift mask blank and method for manufacturing phase shift mask |
| TWI480675B (en) * | 2004-03-31 | 2015-04-11 | Shinetsu Chemical Co | Halftone phase shift mask blank, halftone phase shift mask, and pattern transfer method |
| JP4933753B2 (en) * | 2005-07-21 | 2012-05-16 | 信越化学工業株式会社 | Phase shift mask blank, phase shift mask, and manufacturing method thereof |
| JP4695964B2 (en) * | 2005-11-09 | 2011-06-08 | アルバック成膜株式会社 | Gray tone mask and manufacturing method thereof |
| TWI498667B (en) * | 2005-12-26 | 2015-09-01 | Hoya Corp | A mask substrate and a mask for manufacturing a flat panel display device |
| JP4570632B2 (en) * | 2006-02-20 | 2010-10-27 | Ｈｏｙａ株式会社 | Four-tone photomask manufacturing method and photomask blank processed product |
| CN101025564B (en) * | 2006-02-20 | 2010-12-15 | Hoya株式会社 | Four-gradation photomask manufacturing method and photomask blank for use therein |
| KR100886802B1 (en) * | 2006-03-30 | 2009-03-04 | 주식회사 에스앤에스텍 | Blankmask and Transmittance Modulation Slit Mask using the same, and Manufacturing Method thereof |
| KR101329525B1 (en) * | 2006-10-04 | 2013-11-14 | 주식회사 에스앤에스텍 | Gray-tone Blank Mask and Gray-tone Photomask, the Manufacturing method of them |
| JP4848932B2 (en) * | 2006-11-13 | 2011-12-28 | 大日本印刷株式会社 | Tone mask for proximity exposure |
| US20100294651A1 (en) * | 2007-10-12 | 2010-11-25 | Ulvac Coating Corporation | Process for producing gray tone mask |
| JP5219201B2 (en) * | 2008-07-31 | 2013-06-26 | Ｈｏｙａ株式会社 | Photomask, photomask blank, photomask manufacturing method, and pattern transfer method |
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| JP5121020B2 (en) | 2013-01-16 |
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