TW200809393A - Mask blank and photomask - Google Patents
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- TW200809393A TW200809393A TW096116826A TW96116826A TW200809393A TW 200809393 A TW200809393 A TW 200809393A TW 096116826 A TW096116826 A TW 096116826A TW 96116826 A TW96116826 A TW 96116826A TW 200809393 A TW200809393 A TW 200809393A
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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
- G03F1/38—Masks having auxiliary features, e.g. special coatings or marks for alignment or testing; Preparation thereof
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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
- G03F1/50—Mask blanks not covered by G03F1/20 - G03F1/34; Preparation thereof
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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
- G03F1/66—Containers specially adapted for masks, mask blanks or pellicles; Preparation thereof
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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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- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Preparing Plates And Mask In Photomechanical Process (AREA)
- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
Abstract
Description
200809393 九、發明說明： 【發明所屬之技術領域】 本發明係關光罩基底及光罩，特別是關於製造fpd裝 置之光罩基底（光罩用的基底），使用所關光罩基底製造之 光罩（轉印光罩）等。 【先前技術】 近年，在於大型FPD用光罩的領域，試圖使用具有半 透光性區域（所謂灰階部）之灰階光罩，減少光罩片數（非 專利文獻1)。 在此，灰階光罩，係如圖6(1)及圖7(1)所示，於透 明基板上，具有遮光部1、穿透部2及半透光性區域之灰 階部3。灰階部3，具有調整穿透量之機能，例如，如圖 6(1)所示形成灰階光罩用半透光性膜（半透光性膜）3a， 之區域，或者，如圖7(1)所示形成灰階圖案（使用灰階光 罩之大型LCD用曝光機之解析度極限以下的細微遮光圖案 3a及細微穿透部3b)之區域，減低穿透該等區域之光之穿 透量減低由該區域之照射量，將對應所關區域之光阻劑之 顯影後的之減膜之膜厚控制為所期望之值為目的形成。 將大型灰階光罩，搭載於鏡投影方式或使用透鏡之透 鏡投影方式之大型曝光裝置使用時，由於通過灰階部3之 曝光光全體而言曝光量會不足，故經由灰階部3曝光之正 型光阻劑的膜厚只會變薄而殘留於基板上。即，光阻劑會 因曝光量的不同而對應通常的遮光部1之部分與對應灰階 2190-8838-PF 5 200809393 部3之部分對顯影液之溶解性產生差異，故顯影後的光阻 劑f狀將如圖6(2)及圖7(2)所示，對應通常的遮光部i 之部分Γ成例如約1 # m，對應灰階部3之部分3，例如 =約，〇.4〜0.5# m，對應穿透部2之部份成沒有光阻劑的部 分2’ 。然後，在沒有光阻劑的部分2，進行被加工基板 之第1蝕刻，將對應灰階部3之薄的部分3，之光阻劑以 灰化等去除以此部分進行第2蝕刻，以丨片光罩進行先前 的光罩2片份的步驟，減少光罩片數。 [非專利文獻 1]月刊 FPD Intelligence，p. 31-35、 1999年5月 [非專利文獻2 ]「光罩技術的故事」，田邊功、法元 盛久、竹铯洋著，工業調查會刊，「第4章LCD用光罩之 實際」P. 151-180 【發明内容】 [發明所欲解決的課題] 然而，製造微處理器、半導體記憶體、系統LSI等半 $體元件之LSI用光罩’最大為6英忖（132 mm)四方程度 而相對較小型，多搭載於以步進曝光（投影曝光）方式之縮 小投影曝光裝置使用。又，形成於LSI用光罩上之光罩圖 案之最小線寬實現0· 26 // m程度（形成於晶圓上之圖案的 最小線寬為0· 07 // m)。 於所關LSI用光罩之製造，由於一般需要形成上述之 高精細圖案，故於光罩基底上塗佈電子線光阻劑（光阻劑 2190-8838-PF 6 200809393 膜厚N通常相對較小為·，〇nm)，進行電子描緣，形成 先阻劑圖案，將該光阻劑圖案作為掩模形成光罩圖案。 再者，在於製造LSI用光罩之小型光罩基底，綜合考 =1、型基底之塗佈精度、量產性、成本等，以旋轉塗佈 塗佈光阻劑。 對此，FPD(平面顯示器)用大型光單，最小也有· •程度(最大為122。_咖職程度)而相對較大 =搭载於鏡投影（以掃描曝光方式之等倍投影曝光）方式 或透鏡投影方式之曝弁奘罟蚀 ^曝九裝置使用。又，形成於FPD用大型 用圖案之最小線寬& _程度以下，形成於被轉印 用大里破璃基板上之圖案之最 田 深見岣為2〜3 // m程度， ”取先端LSI的最小線寬相比較大。 於所關FPD用大型光罩之製造，係於光罩基底上塗佈 ^劑（纽劑膜厚N通常相對較大為刪⑷，進行雷射 掃“，形成光阻劑圖案，將 〃將該先阻劑圖案作為掩模形成光 卓圖案。 者虐：者》製造PM用大型光罩之大型光罩基底，綜合 ^對大型光/基底之塗佈精度、良率等，以狹縫狀的喷 ^ 土板上~ 光阻劑之狹縫式光阻劑塗佈裝置塗 佈光阻劑。 4 1 土 ，以，’於FPD用大型光罩基底及光罩，根據光罩尺 寸的相異專’使用與用止罢 光阻劑塗佈方法)或不 +同的製程(描繪方法或 „. /不冋條件（光阻劑之種類或光阻劑膜 將該等製程或條件需要檢討使用於FPD用大型光罩200809393 IX. Description of the Invention: [Technical Field] The present invention relates to a reticle substrate and a reticle, and more particularly to a reticle substrate (a substrate for a reticle) for manufacturing an fpd device, which is manufactured using the reticle substrate Photomask (transfer mask), etc. [Prior Art] In the field of a large-sized FPD mask, in recent years, it has been attempted to reduce the number of masks by using a gray scale mask having a semi-translucent region (so-called gray scale portion) (Non-Patent Document 1). Here, as shown in Fig. 6 (1) and Fig. 7 (1), the gray scale mask has a light shielding portion 1, a penetration portion 2, and a gray scale portion 3 of a semi-translucent region on the transparent substrate. The gray scale portion 3 has a function of adjusting the amount of penetration. For example, as shown in FIG. 6 (1), a region of a semi-transmissive film (semi-transmissive film) 3a for a gray scale mask is formed, or, as shown in FIG. The area of the gray-scale pattern (the fine light-shielding pattern 3a and the fine-penetrating portion 3b below the resolution limit of the exposure machine for a large LCD using a gray scale mask) is formed in 7(1), and the light penetrating the areas is reduced. The amount of penetration is reduced by the amount of irradiation in the region, and the film thickness corresponding to the developed film of the photoresist in the closed region is controlled to a desired value. When a large-scale gray scale mask is used in a large-scale exposure apparatus using a mirror projection method or a lens projection method using a lens, since the exposure amount is insufficient due to the entire exposure light of the gray scale portion 3, exposure is performed via the gray scale portion 3 The film thickness of the positive photoresist is only thinned and remains on the substrate. That is, the photoresist may have a difference in the solubility of the developer corresponding to the portion of the normal light-shielding portion 1 and the portion corresponding to the gray scale 2190-8838-PF 5 200809393 due to the difference in the amount of exposure, so the photoresist after development As shown in Fig. 6 (2) and Fig. 7 (2), the portion f corresponding to the normal light-shielding portion i is, for example, about 1 # m, corresponding to the portion 3 of the gray-scale portion 3, for example, about 〇. 4 to 0.5 # m, corresponding to the portion of the penetrating portion 2 into a portion 2' having no photoresist. Then, in the portion 2 where the photoresist is not provided, the first etching of the substrate to be processed is performed, and the thin portion 3 corresponding to the gray scale portion 3 is removed by ashing or the like to perform the second etching. The reticle mask performs the previous steps of the reticle 2 to reduce the number of reticle sheets. [Non-Patent Document 1] Monthly FPD Intelligence, p. 31-35, May 1999 [Non-Patent Document 2] "The Story of Photomask Technology", Tanabe Satoshi, Fasumi Masahiro, Takenaka, Industrial Research Journal "Chapter 4: The actual use of the mask for LCDs" P. 151-180 [Explanation] [Problems to be solved by the invention] However, it is used to manufacture LSIs such as microprocessors, semiconductor memories, and system LSIs. The mask 'is a maximum of 6 inches (132 mm) in a square shape and is relatively small, and is often used in a reduced projection exposure apparatus using a step exposure (projection exposure) method. Further, the minimum line width of the mask pattern formed on the LSI photomask is 0.26 // m (the minimum line width of the pattern formed on the wafer is 0·07 // m). In the manufacture of the LSI reticle, it is generally required to form the above-mentioned high-definition pattern, so that an electron-line photoresist is coated on the reticle substrate (photoresist 2190-8838-PF 6 200809393 film thickness N is generally relatively relatively Small, 〇nm), an electronic trace is formed to form a first resist pattern, and the photoresist pattern is used as a mask to form a mask pattern. Further, in order to manufacture a small mask base for a LSI photomask, a photoresist is applied by spin coating in consideration of coating accuracy, mass application property, cost, and the like of the mold base. In this case, the FPD (flat-panel display) uses a large optical order, and the minimum is also a degree (maximum of 122._cafe level) and relatively large = mounted on the mirror projection (in the case of scanning exposure mode, etc.) The lens projection method is used for exposure and exposure. In addition, the minimum line width of the FPD large-size pattern is equal to or less than the minimum line width of the FDD large-size pattern, and the pattern of the pattern formed on the large-sized glass substrate for transfer is 2 to 3 // m. The minimum line width is relatively large. In the manufacture of a large reticle for the FPD, the coating is applied to the reticle substrate (the film thickness N is usually relatively large (4), and the laser sweep is performed. The photoresist pattern is formed by using the first resist pattern as a mask to form a light pattern. Abusive: "Making a large mask base for a large photomask for PM, comprehensively coating precision of large light/substrate, For the yield, etc., the photoresist is applied by a slit-type photoresist coating device on a slit-shaped sprayed plate to a photoresist. 4 1 soil, to, 'large reticle base and light for FPD Cover, according to the different size of the mask, 'use and use of photoresist coating method' or not + the same process (drawing method or „. / 不冋 conditions (type of photoresist or photoresist film These processes or conditions need to be reviewed for use in large masks for FPD
2190-8838-PF 7 200809393 基底及光罩時需要檢討起因於基板為大型所產生之問題。 本案之目的，係提案適於FPD用大型光罩之製程（描 、、、曰方式或光阻劑塗佈方法）或不同條件（光阻劑之種類 光阻劑膜厚）之光罩基底及光罩。 $ [用以解決課題的手段] 在上述目的之下，本發明者，銳意研究，進行開發關 於FPD用大型光罩基底纟FpD用大型光罩。結|，發現如 下之情形〇 ^ 口 塗佈於FPD用大型光罩基底上之光阻劑膜厚，大體上 不會產生雷射描繪波長之駐波地，現行，設定為約 1 0 0 0nm但疋，使用上述狹縫式光阻劑塗佈裝置形成1光 阻劑膜之面内膜厚之離散n，相對較大，光阻劑膜厚之面 内膜厚離散寬2n，有成與雷射描繪波長L之半波長丨/儿 同耘度之情形。此時，於面内產生光阻劑膜厚成為半波長 之整數倍之膜厚處，在成所關半波長之整數倍之膜厚處， 入射光阻劑膜通過抗實劑膜之雷射描繪光之入射光，與通 過光阻劑膜於遮光性膜之膜面反射之雷射描繪光的反射 光，互相干擾產生相對振幅強度較小的駐波，並且於遮光 性膜之膜面反射之雷射描繪光之反射光通過光阻劑膜於 光阻劑膜之膜面反射，成如在成為半波長的整數倍之距離 存在相對的壁之情形才目㈤，故每次反覆反射則作為合成波 產生相對振幅強度較大的駐波，發生可當作共振之現象。 如此之特殊的駐波稱為基準共振模式。 於FPD用大型光罩基底，光阻劑膜厚成為半波長之整 2190-8838-PF 8 200809393 數倍之膜厚處所產生的基準共振模式之駐波，係基於在基 準共振模式之駐波之峰所產生之光阻劑的感光作用，將光 阻劑圖案平面視時本發明者們發現會在光阻劑圖案邊緣 產生凹凸（鑛齒），然後，於FPD用大型光罩基底，欲將光 阻d圖案作為光罩藉由濕式㈣形成下世代規格之1 ^ 以下的光罩圖案(例如，…PD用曝光機之解析極限以 下的細微遮光圖案及細微穿透部所構成之圖案)時，產生 超過〇._之鑛齒’發現該鑛齒將成FPD裝置之顯示晕 入：在於FPD用大型光罩，由圖案的細微化，及圖案 、、度提升之點’涊為需要光阻劑膜厚之進一步薄膜化： π亦於光阻劑膜厚N與面内膜厚的離散之範圍，在 波長之半波長之整數倍之媒厚處，因基準共 振权式之駐波於光阻劑 F⑽置之顯示晕之原因邊緣產生凹凸(鑛齒)，成為 光性=本面=者們，、為解決上述問題，發現使上述遮 模式之駐汸旦率成為對於大體上可迴避因基準共振 :叫 < 影響對光阻劑圖案所 綠波長之膜面反射率為有效，完成本發明雷射描 本發明方法，具有以下構成。 性基= :置製造用光罩基底，其係於透光 射描緣用光阻劑膜者:其=在:上述遮光性膜上形成雷 上述遮光性膜，係對雷射騎波長之膜面反射率控制2190-8838-PF 7 200809393 The substrate and the mask need to be reviewed for problems caused by the large substrate. The purpose of this case is to propose a mask base suitable for the process of FPD large-scale photomask (drawing, sputum, or photoresist coating method) or different conditions (resistant type photoresist film thickness). Photomask. [Means for Solving the Problem] Under the above object, the inventors of the present invention have made intensive research and development of a large-sized photomask for FPD for a large-sized mask base for FPD. In the case of the junction, the film thickness of the photoresist coated on the large mask substrate for the FPD is found to be substantially no standing wave of the laser drawing wavelength. Currently, it is set to about 1000 nm. However, the slit n-type photoresist coating device is used to form the dispersion n of the in-plane film thickness of the photoresist film, which is relatively large, and the in-plane film thickness of the photoresist film thickness is 2 n wide and wide. The laser depicts the half-wavelength 丨/child of the wavelength L. At this time, in the in-plane film thickness at which the photoresist film thickness becomes an integral multiple of a half wavelength, the incident photoresist film passes through the laser of the anti-solid film at a film thickness which is an integral multiple of the half wavelength of the off-half wavelength. The incident light that depicts the light and the reflected light of the laser light that is reflected by the photoresist film on the film surface of the light-shielding film interfere with each other to generate a standing wave having a relatively small amplitude intensity, and is reflected on the film surface of the light-shielding film. The laser reflects that the reflected light of the light is reflected by the photoresist film on the film surface of the photoresist film, so that if there is a relative wall at a distance that is an integral multiple of a half wavelength, (5), each reflection is repeated. As a composite wave, a standing wave having a relatively large amplitude intensity is generated, and a phenomenon that can be regarded as resonance occurs. Such a special standing wave is called a reference resonance mode. For the FPD large-scale mask substrate, the photoresist has a thickness of half the wavelength of the 2190-8838-PF 8 200809393 multiple times. The standing wave of the reference resonance mode is based on the standing wave in the reference resonance mode. The sensitizing effect of the photoresist produced by the peak, when the photoresist pattern is viewed in a plane, the inventors have found that unevenness (mineral teeth) is generated at the edge of the photoresist pattern, and then, for the FPD, a large reticle substrate is desired. The photoresist d pattern is formed as a mask by a wet pattern (4) to form a mask pattern of 1^ or less of the next generation specification (for example, a pattern of a fine light-shielding pattern and a fine penetration portion below the analysis limit of the exposure machine for PD). At the time, the mineral tooth that produced more than 〇._ found that the ore tooth will become the display of the FPD device: in the FPD with a large mask, the pattern is subtle, and the pattern, the degree of improvement, '涊Further thinning of the resist film thickness: π is also in the range of the thickness of the photoresist film N and the in-plane film thickness, at a medium thickness of a half wavelength of the wavelength, due to the standing wave of the reference resonance weight Photoresist F (10) placed to show the cause of halo Concavities and convexities (mineral teeth) become lightness = this side =, in order to solve the above problem, it is found that the above-mentioned masking mode has become a substantially repellent due to reference resonance: called < influence on the photoresist The film surface reflectance of the green wavelength of the pattern is effective, and the method of the invention of the present invention is completed, and has the following constitution. Substrate=: A photomask substrate for manufacturing is used for a photoresist film for a light-transmitting projection edge: it is: a light-shielding film formed on the above-mentioned light-shielding film, and a film for laser riding wavelength Surface reflectance control
2190-8838-PF 9 200809393 為15%以下之膜。 (構成2) 構成1所述的FPD裝置製造用光罩基底，其中上述雷 射描繪波長，係選自由35Onm〜50Onm之波長範圍之波長。 (構成3) 構成1或2所述的FPD裝置製造用光罩基底，其中上 述遮光性膜，至少具有反射防止層，及控制該反射防止層 之結晶性之結晶性控制層。 (構成4) 構成1至3所述的FPD裝置製造用光罩基底，其中上 述遮光性膜之膜面反射率成最小之最小反射率存在於 350nm〜500nm之波長範圍。 (構成5) 構成1至4所述的FPD裝置製造用光罩基底，其中上 述遮光性膜之反射率曲線如描緣向 (構成6 ) 下凸之曲線地構成。 、構成1至5所述的FPD裝置製造用光罩基底，其中於 上述遮光性膜上具有雷射描繪用光阻劑膜。 (構成7) 構成6之所述的 FPD裝置製造用光罩基底，其中上述 光阻劑膜之膜厚， (構成8 ) 係 400〜1200nm 。 構成6之所述的 光阻劑膜之膜厚，位 FPD裝置製造用光罩基底，其中上述 係 400〜80Onm 〇2190-8838-PF 9 200809393 is a film of 15% or less. (Configuration 2) The reticle base for manufacturing an FPD device according to Aspect 1, wherein the laser drawing wavelength is selected from wavelengths in a wavelength range of 35 Onm to 50 Onm. (Aspect 3) The photomask substrate for manufacturing an FPD device according to the above aspect 1, wherein the light-shielding film has at least an antireflection layer and a crystallinity control layer for controlling crystallinity of the antireflection layer. (Configuration 4) The photomask substrate for manufacturing an FPD device according to any one of the above-described first to third aspect, wherein the minimum reflectance of the light-shielding film having a minimum surface reflectance is in the wavelength range of 350 nm to 500 nm. (Configuration 5) The reticle base for manufacturing an FPD device according to any one of the first to fourth aspects, wherein the reflectance curve of the light-shielding film is configured such that a curve of the slanting direction (constitution 6) is convex. The photomask substrate for manufacturing an FPD device according to any one of the first to fifth aspect, wherein the light-shielding film has a photoresist film for laser drawing. (Structure 7) The photomask substrate for manufacturing an FPD device according to Aspect 6, wherein the film thickness of the photoresist film (configuration 8) is 400 to 1200 nm. The film thickness of the photoresist film as described in the sixth aspect, the photomask substrate for manufacturing the FPD device, wherein the above-mentioned system is 400 to 80 nm.
2190-8838-PF 10 200809393 (構成9) 一種製造FPD裝置之光罩，苴特矜犬认 士 充旱，、特徵在於：使用構成6 至8所述的FPD裝置製造 衣置用先罩基底，對上述光阻劑膜進 行雷射描繪，形成光阻劑圖荦， ⑷α系將该先阻劑圖案作為掩膜 形成光罩圖案而製造。 、 [發明之效果；| 根據本發明，可提供適於FPD用大型光罩之製程（描 緣方法或光阻劑塗佈方法）或相異條件（光阻劑之種類或 光阻劑膜厚）之光罩基底及光罩。 【實施方式】 以下詳細說明本發明。 本發明之FPD裝置製造用光罩基底， 係於透光性基板上，至少具有遮光性膜，於上述遮光 性膜上形成雷射描相光阻劑膜者，其特徵在於··上述遮 光性膜，係對雷射描繪波長之膜面反射率控料15%以下 之膜（構成1)。 於本I明，藉由使對於雷射描繪波長之膜面反射率為 1 5%以下，可防止因基準共振模式之駐波產生光阻劑圖案 邊緣之凹凸（鋸#)。藉此，可防止將光阻劑圖案作為掩膜 藉由濕式蝕刻形成下世代規格之"数米以下的光罩圖案 (例如，大型FPD用曝光機之解析極限以下的細微遮光圖 案及細微穿透部所構成之圖案）時，i生㈣〇 ι "之錯 齒，然後因該鋸齒產生FPD裝置之顯示暈。 2190-8838-PF 11 200809393 又，圖案的細微化，與提升圖案精度之點，認為需要 光阻劑膜之進一步薄膜化，（例如，400nm〜8〇〇nm)，此時， 亦可防止，因基準共振模式之駐波於光阻劑圖案邊緣產生 凹凸（鑛齒），然後因該鑛齒產生FPJ)裝置之顯示暈。 於本發明，上述遮光性臈，以對於雷射描繪波長之膜 面反射率控制成12%以下，進一步成1〇%以下之膜更佳。' 於本發明，上述雷射描繪波長，係由35〇nm5〇〇⑽之 波長範圍選擇（構成2)。例如，作為雷射描繪波長，可舉， 365nm、405nm、413nm、436nm、442nm、488nm。 又，於本發明，作成於上述遮光性膜上具有雷射描繪 用光阻劑膜之具有光阻劑膜之FpD裝置製造用光罩基底 (構成3)。此時，於本發明，上述光阻劑膜之膜厚:係 4〇(M2GGnm(構成4)，由圖案的細微化，及提升圖案精度 之點，最好以400〜800nm為佳（構成5)。這是因為要避免 如上所述，於FPD用大型光罩基底上，形成所關膜厚範圍 之相對較厚之光阻劑膜（例如，9〇G.12G〇nm)時，由於起 因於抗時劑膜之膜厚之面内離散寬度2…會產生因基 準共振模式之駐波對光阻劑膜圖案造成影響之問題。又一 原因為由圖案的細微化，及提升圖案精度之點，認為光阻 膜化’所以將該光阻劑膜薄膜化時，要謀求* 力长共振模式之駐波對光阻劑膜圖案造成影響，也 力求肩除薄臈化之限制。 於本發明’由具有向—方向延伸之 噴嘴吐出光阻劑液，同拉伯為I 促1、、、，口口之 @時使㈣對遮光性膜表面向與該一2190-8838-PF 10 200809393 (Structure 9) A photomask for manufacturing an FPD device, which is characterized in that the FPD device of the above-described 6 to 8 is used to manufacture a hood substrate for clothes, The photoresist film is subjected to laser drawing to form a photoresist pattern, and (4) α is produced by forming the mask pattern using the resist pattern as a mask. [Effects of the Invention; | According to the present invention, a process suitable for a large photomask for FPD (a method of drawing or a photoresist coating method) or a different condition (a type of a photoresist or a film thickness of a photoresist) can be provided. The reticle base and the reticle. [Embodiment] Hereinafter, the present invention will be described in detail. The mask base for manufacturing the FPD device of the present invention is a light-transmitting substrate, and has at least a light-shielding film, and a laser-patterned photoresist film is formed on the light-shielding film, and the light-shielding property is characterized by The film is a film having a film surface reflectance of 15% or less of the laser drawing wavelength (constitution 1). According to the present invention, by making the film surface reflectance for the laser drawing wavelength 15% or less, it is possible to prevent the unevenness (saw #) of the edge of the photoresist pattern from being generated by the standing wave in the reference resonance mode. Therefore, it is possible to prevent the mask pattern from being formed into a mask of a next generation size by a wet etching method as a mask (for example, a fine shading pattern below the resolution limit of an exposure machine for a large FPD and a subtle When the pattern formed by the penetrating portion is i, the wrong tooth of the (4) 〇ι " is generated, and then the display halo of the FPD device is generated by the saw tooth. 2190-8838-PF 11 200809393 In addition, the fineness of the pattern and the improvement of the pattern accuracy are considered to require further thinning of the photoresist film (for example, 400 nm to 8 〇〇 nm), and at this time, it is also prevented. The standing wave due to the reference resonance mode generates irregularities (mineral teeth) at the edge of the photoresist pattern, and then the display faint of the FPJ) device is generated due to the ore teeth. In the present invention, the light-shielding property is preferably controlled to 12% or less with respect to the film reflection wavelength of the laser drawing wavelength, and more preferably 1% by weight or less. In the present invention, the above-described laser drawing wavelength is selected from the wavelength range of 35 〇 nm 5 〇〇 (10) (constitution 2). For example, as the laser drawing wavelength, 365 nm, 405 nm, 413 nm, 436 nm, 442 nm, and 488 nm can be mentioned. Further, in the present invention, a photomask substrate for manufacturing an FpD device having a photoresist film having a photoresist film for laser drawing is provided on the light-shielding film (Configuration 3). In this case, in the present invention, the film thickness of the photoresist film is 4 〇 (M2GGnm (Structure 4), and the fineness of the pattern and the improvement of the pattern accuracy are preferably 400 to 800 nm (constitution 5). This is because, as mentioned above, when a relatively thick photoresist film (for example, 9 〇 G.12 G 〇 nm) is formed on a large reticle substrate for FPD, due to the cause The discrete width 2 in the film thickness of the anti-time agent film causes a problem that the standing wave of the reference resonance mode affects the photoresist film pattern. Another reason is the miniaturization of the pattern and the improvement of the pattern precision. When the photoresist film is thinned, it is necessary to achieve a problem in which the standing wave of the long-resonant resonance mode affects the pattern of the photoresist film, and it is also required to remove the limitation of thinning. The invention discloses that the photoresist liquid is ejected from a nozzle having a direction extending in the direction of the light, and the same as that of Rab, I, and (@) the surface of the light-shielding film and the
2190-8838-PF 12 200809393 方向交又之方向相對移動形成光阻劑膜，藉由所謂狹 佈裝置對大面積的遮光性膜面上塗佈光阻劑時特別有 利。又，於本發明，上述狹縫塗佈裝置，係對於朝下 之基板，藉由毛細狀之喷嘴使用毛細管現象將上升之光阻 劑液使噴嘴前端對基板掃描，塗佈光阻劑之裝置（來 如圖3)時’特別有利。此係，於該等情形，因遮光性膜之 表面狀態等存在與雷射掃描波長L之半波長1/2L同程产 之面内膜厚離散寬度2n，而產生對光阻劑膜圖案造成^ 之問題的之可能性高。 曰 再者，對於各種膜材料研究結果，發現如下情形。 (1)若為鉻酸系的反射防止膜（例如Cr〇膜單層等）， 則發現由於在膜中含〇(由於膜中的〇多），於雷㈣㈣ 長（例如，365mn、405mn、413nm、436mn、442mn)之波段， 再者於包含所關波段之更廣的波段之分光反射率之曲線 (傾斜）急，有分光反射率之變動變大之傾向。 (1 1 )相較於鉻酸膜系的反射防止膜，鉻酸氮化膜的反 射防止膜（例如Cr〇N)，於雷射描繪波長（例如，365測、 405nm、413nm、436nm、442nm)之波段，再者於包含所關 '皮#又之更廣的波段之分光反射率之曲線（傾斜）緩，分光反 射率之變動變小而佳。 惟，對於雷射描繪波長之膜面反射率之下限的追求， 或為解决因膜面之表面狀態之離散之狹縫塗佈之面内離 散之圖案鋸齒等對光阻劑膜圖案造成影響之問題，並不是 使用任何一種鉻酸氮化膜系之反射防止膜都適於達成目2190-8838-PF 12 200809393 The direction of the direction of the movement is relatively shifted to form a photoresist film, which is particularly advantageous when a photoresist is applied to a large-area light-shielding film surface by a so-called slit device. Further, in the present invention, the slit coating apparatus is a device for applying a photoresist to a substrate which is raised by a capillary nozzle using a capillary phenomenon by a capillary nozzle, and a tip end of the nozzle is scanned against the substrate. (come to Figure 3) is particularly advantageous. In this case, due to the surface state of the light-shielding film or the like, there is an in-plane film thickness dispersion width 2n which is produced by the same half-wavelength 1/2L of the laser scanning wavelength L, resulting in a pattern of the photoresist film. ^ The possibility of the problem is high.曰 Furthermore, for the results of various membrane materials, the following cases were found. (1) In the case of a chromic acid-based antireflection film (for example, a Cr ruthenium film single layer or the like), it is found that ruthenium (four) is long (for example, 365 mn, 405 mn, due to ruthenium contained in the film (due to the ruthenium in the film). In the band of 413 nm, 436 mn, and 442 mn, the curve (inclination) of the spectral reflectance of the wider band including the wavelength band is increased, and the variation of the spectral reflectance tends to be large. (1 1 ) The anti-reflection film of the chromic acid nitride film (for example, Cr〇N) is at a laser drawing wavelength (for example, 365 Å, 405 nm, 413 nm, 436 nm, 442 nm) compared to the chromic acid film-based anti-reflection film. The band of the light beam, and the curve (inclination) of the spectral reflectance of the band including the wider band of the skin is slower, and the variation of the spectral reflectance becomes smaller. However, the pursuit of the lower limit of the film surface reflectance of the laser drawing wavelength, or the in-plane discrete pattern sawtooth of the slit coating due to the surface state of the film surface, affects the photoresist film pattern. The problem is not that any anti-reflective film of chromic acid nitride film is suitable for achieving the goal.
2190-8838-PF 13 200809393 的，並且鉻酸氮化膜系之反射防止膜之下層並不是任何一 種遮光性膜均適於達成所關目的。因此，發現需要找出滿 足適於達成目的之既定的條件之遮光性膜而使用為佳。 為達成上述兩目的，由於藉由於上述鉻酸氮化膜系反 射防止膜之下層，形成鉻氮化系膜（例如，CrN)，可使形 成於其上層之膜之結晶性細微化，且形成均勻的膜，故遮 光性膜的表面狀態安定，於藉由狹縫塗佈形成光阻劑膜之 、月形亦可抑制面内膜厚之離散。再者，可追求對雷射描繪 波長之膜面反射率之下限，可使分光反射率之變動幅度小 而佳。 於製造關於本發明之FPD裝置之光罩基底及光罩，包 & ;透月性基板上，至少具有遮光性膜之形態。具體而 包含例如’如圖4所示，於透光性基板10上形成遮 光陸膜12，對此施以圖案化，形成灰階圖案i 2a與通常的 遮光性臈圖案12b而成之形態。 、、於製造關於本發明之FPD裝置之光罩基底及光罩，上 ，遮光H膜，最好是將該遮光性膜之膜面反射率成最小之 最J反射率控制於35〇nm〜45〇nm之波長範圍之膜。 -理由’係因為將遮光性膜之膜面反射率成最小之最 小反射率（即底峰的位置）控制成存在於35()nm〜45_之波 長範圍之膜’在製造為製造FPD裳置之光罩時之一般使用 的雷射描緣波長，對分光曲線伴隨製程變動向上下左右方 向之位移’分光反射率值很少大大地變動。 作為如上述，對分光曲線伴隨製程變動向左右方向之2190-8838-PF 13 200809393, and the underlying layer of the anti-reflection film of the chromic acid nitride film system is not suitable for the purpose of achieving any of the light-shielding films. Therefore, it has been found that it is preferable to use a light-shielding film which satisfies the predetermined conditions suitable for the purpose. In order to achieve the above two objectives, the chromic nitride film (for example, CrN) is formed by the chromic acid nitride film-based anti-reflection film underlayer, and the crystallinity of the film formed on the upper layer can be made fine and formed. Since the film is uniform, the surface state of the light-shielding film is stabilized, and the moon-shaped shape of the photoresist film formed by the slit coating can also suppress the dispersion of the in-plane film thickness. Further, the lower limit of the film reflectance of the laser drawing wavelength can be pursued, and the variation range of the spectral reflectance can be made small. The reticle substrate and the photomask for manufacturing the FPD device of the present invention have a shape of at least a light-shielding film on the moon-permeable substrate. Specifically, for example, as shown in Fig. 4, the light-blocking land film 12 is formed on the light-transmitting substrate 10, and patterned to form a gray-scale pattern i 2a and a normal light-shielding ruthenium pattern 12b. In order to manufacture the reticle base and the reticle of the FPD device of the present invention, the light-shielding H film is preferably controlled to have a minimum J reflectance of the opaque film at 35 〇 nm~ A film in the wavelength range of 45 〇 nm. - Reason 'Because the minimum reflectance (ie, the position of the bottom peak) at which the film surface reflectance of the light-shielding film is minimized is controlled to be a film present in the wavelength range of 35 () nm to 45 mm. The wavelength of the laser beam used in the case of the photomask is small, and the spectral reflectance value of the spectroscopic curve varies greatly with the fluctuation of the process in the up, down, left, and right directions. As described above, the spectroscopic curve is accompanied by the process variation in the left-right direction.
2190-8838-PF 14 200809393 位移其分光反射率值很少大大地變動（位移少）之遮光性 +、至^以控制上層膜之結晶性之結晶性控制層，及具有 遮光機能之下層部與具有反射防止機能之上層部構成之 遮光性膜為佳。 在此，結晶性控制層，係控制形成於其上之膜之結晶 性之部分。具有遮光機能之下層部，係遮光性能高的部分 可顯現所要求之遮光性能之大部分或全部之部分。又，具 f反射防止機能之上層部，係形成於具有遮光機能之下層 部之上，減少具有遮光機能之下層部之反射率，顯現反射 防止機能之部分。 …於製造關於本發明之FPD裝置之光罩基底及光罩，上 述遮光性膜’係以控制結晶性之氮化鉻系之結晶性控制 層及具有it光機能之鉻或碳化絡系之下層#肖具有反射 防止機能之氮氧化鉻系上層部構成，上述結晶性控制層、 下層部及上層部，以滿足上述要件作光學設計，而作成為 佳。 其理由，係因為由該等材料系構成之膜（例如，以CrN 結晶性控制層収遮光性層（下層部）/㈣反射防止層 (上層。卩）構成之膜、CrN結晶性控制層MrCN遮光性層（下 層部）/CrON反射防止層（上層部）構成之膜等），相較於其 他的材料系之膜，藉由膜組成的調整、製造條件、製造裝 置等的選定及控制，由該等之膜質控制，遮光性膜之材料 等，底峰位^，膜構成等，於橫跨波長35〇nm〜45〇nm之波 長波&，谷易得到控制遮光性膜之膜面反射率之變動寬幅2190-8838-PF 14 200809393 Displacement The spectral reflectance value of the displacement is rarely changed greatly (less displacement), the crystallographic control layer to control the crystallinity of the upper film, and the layer under the shading function A light-shielding film having a layer portion above the reflection preventing function is preferred. Here, the crystallinity controlling layer controls the crystallinity of the film formed thereon. The portion having the lower portion of the shading function and having a high light-shielding property can exhibit most or all of the required shading performance. Further, the upper portion of the f-reflection prevention function is formed on the layer below the shading function, and the portion having the reflectance of the layer under the shading function is reduced, and the reflection preventing function is exhibited. In order to manufacture a mask base and a mask for the FPD device of the present invention, the light-shielding film ' is a chromium nitride-based crystallized control layer for controlling crystallinity and a chromium or carbonized underlayer having an optical function. #肖 has a structure of an upper layer of a nitrous oxide oxide having a reflection preventing function, and the crystallizing control layer, the lower layer portion, and the upper layer portion are preferably optically designed to satisfy the above requirements. The reason is a film composed of these materials (for example, a film composed of a CrN crystallizable control layer, a light-shielding layer (lower layer portion), a (four) anti-reflection layer (upper layer), and a CrN crystallizable control layer, MrCN. a light-shielding layer (lower layer portion)/a film composed of a CrON reflection preventing layer (upper layer portion), etc., and a film composition adjustment, a manufacturing condition, a manufacturing device, and the like are selected and controlled as compared with other material-based films. Controlled by the film quality, the material of the light-shielding film, the bottom peak position, the film structure, etc., across the wavelength wavelength of 35 〇 nm to 45 〇 nm wavelength, and the film surface of the control light-shielding film is obtained. Wide range of reflectivity
2190-8838-PF 15 200809393 為未滿2%之膜，藉此，可得對分光曲線伴隨製程變 右方向之位移，分光反射率值不會 〇左 膜。又，於所關構成之膜，可對雷射描綠波長追求膜面二 射率之下限，以狭縫塗佈機形成光阻劑膜時亦可、 膜厚之離散。 於製造關於本發明之FPD裝置之光罩基底及光罩，將 上述遮光性膜藉由線内型_置連續形成為由於藉 由線内型減鍍裝置連續成膜之上述結晶性控制層,遮二 層（下層部）/反射防止層（上層部）所構成之膜，於各臈之 界面不會形成氧化層，故可嚴密地控制光學特性射 等）。 千 於製造關於本發明之FPD裝置之光罩基底及光罩，包 含於透光性基板上具有灰階光罩用半透光性膜與遮光性 膜之形態。具體而言’包含例如，圖5所#，於透光性基 板10上將灰階光罩用半透光性膜丨丨及遮光性膜i 2以此 順序形成，施以該等膜之圖案化，形成灰階光罩用半透光 I*生膜圖案與遮光性膜圖案而成之半透光性膜下置（先置） 型之灰階光罩等之形態。 在此’作為半透性膜之材料，含有Mo與Si之MoSi 系材料，或金屬及矽（MSi、M ·· M〇、Ni、w、Zr、Ti、Cr、2190-8838-PF 15 200809393 is a film that is less than 2%. By this, the splitting curve can be changed in the right direction with the process, and the spectral reflectance value will not be in the left film. Further, in the film which is closed, the lower limit of the film surface dimming rate can be obtained for the laser green wavelength, and the film thickness can be dispersed when the photoresist film is formed by the slit coater. In order to manufacture the mask base and the photomask of the FPD apparatus of the present invention, the light-shielding film is continuously formed by the in-line type to be the above-mentioned crystallizable control layer continuously formed by the in-line type plating apparatus. The film formed by the second layer (lower layer portion) and the antireflection layer (upper layer portion) does not form an oxide layer at the interface of each of the layers, so that optical characteristics can be strictly controlled. The reticle base and the reticle for manufacturing the FPD device of the present invention are included in the form of a semi-transmissive film for a gray scale mask and a light-shielding film on the light-transmitting substrate. Specifically, for example, the light-transmissive substrate 10 is formed on the light-transmissive substrate 10 by using the semi-transmissive film 丨丨 and the light-shielding film i 2 in this order, and the patterns of the films are applied. In the form of a semi-transmissive film under-substrate (pre-set) gray scale mask formed by a semi-transparent I* film pattern and a light-shielding film pattern for a gray scale mask. Here, as a material of the semipermeable membrane, a MoSi-based material containing Mo and Si, or a metal and niobium (MSi, M··M〇, Ni, w, Zr, Ti, Cr,
Ta等之過渡金屬）、氧化氮化之金屬及矽（MSiON)、氧化碳 化之金屬及矽（M〇SiC0)、氧化氮化碳化之金屬及矽 (MSiCON)、氧化之金屬及矽（MSi〇)、氮化之金屬及矽 (MoSiN)等。 2190-8838-PF 16 200809393 於本發明，作為类 可舉合成石英、 可舉酚醛系光阻 戸兩逯明性基板之材料， 納玻璃、無鹼破璃等。 於本么明，作為雷射描繪用光阻劑， 、么明，FPD裝置製造用光罩基底，包含： 射描繪用的光阻劑 '— 性膜之光罩基底。…於透先性基板上具有遮光 於本發明，作為製造FpD裝置之光罩基底及光罩，可 牛製^ LCD(液晶顯示器）、電漿顯示器、有機乩（電致發 光）顯示器等的FPD襄置之光罩基底及光罩。 在此，於LCD製造用光罩，包含於LCD之製造所需之Transition metal of Ta, etc., oxynitride metal and lanthanum (MSiON), oxidized carbonized metal and lanthanum (M〇SiC0), oxynitride carbonized metal and lanthanum (MSiCON), oxidized metal and lanthanum (MSi〇) ), nitrided metal and germanium (MoSiN). 2190-8838-PF 16 200809393 In the present invention, a material for synthesizing quartz or a phenolic photoresist, which is a substrate of phenolic photoresist, nanoglass, alkali-free glass, or the like can be used. In the present invention, as a photoresist for laser light drawing, the mask base for manufacturing an FPD device includes: a photoresist for the image-drawing film. ... having a light-shielding on the transparent substrate, as a mask base and a mask for manufacturing an FpD device, FPD for a liquid crystal display, a plasma display, an organic germanium (electroluminescence) display, etc. The reticle base and the reticle are disposed. Here, the reticle for LCD manufacturing is included in the manufacture of the LCD.
所有光罩，例如，包含形成TFT(薄膜電晶體）、特別是TFT 通道部或接觸孔部、低溫多晶石夕m、彩色據光片、反射 板（黑矩陣）等之光罩。於其他的顯示裝置製造用光罩，包 β於有機EL(電致發光）顯示器、電漿顯示器等之製造所需 之所有光罩。 於製造關於本發明之FPD裝置之光罩，其特徵在於： 使用關於上述本發明之製造Fpd裝置之光罩基底，對於形 成於光罩基底之光阻劑進行雷射描繪，形成光阻劑圖案， 將該光阻劑圖案作為掩膜形成由遮光性膜圖案所構成之 光罩圖案，而製造（構成6)。 以下，進一歩基於實施例更詳細地說明本發明。 (實施例1) 大型玻璃基板（合成石英（QZ)10mm厚，尺寸850mmx 2190-8838-PF 17 200809393 1 200mm)上，使用大型線内型濺鍍裝置，進行以結晶性控 制層、具有遮光機能之下層部、及具有反射防止機能之上 層部構成之遮光性膜之成膜。成膜，係於大型線内型濺鍍 裝置内對於基板搬送方向連續配置之各空間（濺鍍室）各 個配置乾’首先以Ar氣體與N2氣體作為㈣氣體將 CrN層（作為控制之後形成之膜之結晶性為目的之膜）1 μ 埃，接著，以Ar氣體與CL氣體作為濺鍍氣體將CrC層（具 有遮光機能之下層部）650埃，接著以Ar氣體與⑽氣體|乍 為濺鍍氣體將CrON層（具有反射防止機能之上層部）25〇 埃，連續形成，製作光罩基底。再者，各膜分別為組成傾 斜膜。又，CrC層（具有遮光機能之下層部）、因於成膜crN 層或CrON層（具有反射防止機能之上層部）時使用之&氣 體或N0氣體而含n(氮），故於上述crN層、CrC層（具有 遮光機能之下層部）、NCrON層（具有反射防止機能之上層 部）之全部包含Cr與N。 將上述光罩基底之分光反射率線示於圖1。再者，分 光反射率係以分光光度計測定。 於圖1所示分光反射率線，於使用於製造FPD用大型 光罩時之雷射描繪波長（例如，365nm、405nm、4i3nm、 436nm、442nm)之雷射描繪波長波段（350nm〜5〇〇nm)，遮光 性膜之膜面反射率為15%以下。又，包含橫跨上述雷射描 繪波長波段之波長350nm〜450nm之波長波段，膜面反射率 之變動為未滿2%之範圍内（於橫跨波長365nm〜450nm之波 長波段膜面反射率之變動為未滿丨％之範圍内） 2190-8838-PF 18 200809393 、使用以上述製作之光罩基底，使用圖3所示狹縫塗佈 機塗佈酚醛系的雷射描繪用光阻劑，（光阻劑膜厚範圍： l〇〇〇nffl±l〇0nm)，對光阻劑膜以雷射描繪，描繪圖案，藉 由顯影形成光阻劑圖案，將該光阻劑圖案作為掩膜，將3 層構仏之膜（CrN層、CrC層、CrON層）一體以濕式蝕刻圖 案化’製作具有5"m寬的通常的圖t 121)及1//m寬的灰 P白圖案（由大型FPD用曝光機的解析極限以下之細微遮光 圖案及細微透光部所構成之圖案）12a之FpD用大型光罩 (參照圖4)。 於上述步驟，以掃描式電子顯微鏡（SEM)，對光阻劑 圖案、光罩圖案之雙方，觀察通常的圖案、灰階圖案之雙 方，將圖案以平面視時之圖案邊緣之凹凸（所謂鋸齒）為未 滿0 · 1 // m而良好。 使用所得FPD用大型光罩製造之FpD裝置亦沒有顯示 暈而良好。 (實施例2) 於上述實施例1，以Ar氣體與N0氣體作為濺鍍氣體 將CrON層（具有反射防止機能之上層部）以25〇埃的厚度 形成以外，與實施例1同樣地，形成光阻劑圖案，製作F叩 用大型光罩。 於圖2所示分光反射率線，於包含使用於製造FpD用 大型光罩時之雷射描繪波長（例如，365nm、4〇5nm、413_、 436nm 442nm)之雷射描緣波長波段（365nm〜450nm)，遮光 性膜之膜面反射率為12%以下。又，包含上述雷射描繪波 2190-8838-PF 19 200809393 長波段之波長350nm〜45〇nm之波長波段，膜面反射率之變 動為未S 2%之範圍内（於橫跨波長365,45〇關之波長波 段膜面反射率之變動為未滿1%之範圍内）。 彳 以掃描式電子顯微鏡（SEM)，觀察光阻劑圖案、光罩 圖案之雙方’圖案邊緣之凹凸（所謂錯齒）與實施例i同樣 地為未滿0. 1 # m而良好。 (實施例3) 於上述實施例卜以Ar氣體與N0氣體作為濺鍍氣體 將CrON層（具有反射防止機能之上層部）以32〇埃的厚度 形成以外，與實施例i同樣地，形成光阻劑圖案，製作f叩 用大型光罩。 於圖2所示分光反射率線，於包含使用於製造FpD用 大型光罩時之雷射描繪波長（例如，365nm、4〇5nm、413咖、 436nm、442nm)之雷射描繪波長波段（365nm〜45〇nm)，遮光 性膜之膜面反射率為11%以下。又，包含上述雷射描繪波 長波段之波長35 Onm〜45 Onm之波長波段，膜面反射率之變 動為未滿2%之範圍内（於橫跨波長365nm〜45〇nm之波長波 段膜面反射率之變動為未滿丨G/。之範圍内）。 以掃描式電子顯微鏡（SEM)，觀察光阻劑圖案、光罩 圖案之雙方，圖案邊緣之凹凸（所謂鋸齒）與實施例丨同樣 地為未滿〇 · 1 # m而良好。 (實施例4 ) 於上述實施例1，以Ar氣體與NO氣體作為濺鍍氣體 將CrON層（具有反射防止機能之上層部）以2〇〇埃的厚度 2190-8838-PF 20 200809393 形成以外，與實施例1同樣地，形成光阻劑圖案，製作FPD 用大型光罩。 於圖2所示分光反射率線，於包含使用於製造Fp])用 大型光罩時之雷射描繪波長（例如，365_、4〇5_、Ο如m、 436nm、442nm)之雷射描繪波長波段（365nm45〇nm)，遮光 性膜之膜面反射率為14%以下。又，包含上述雷射描緣波 長波段之波長350nm〜450nm之波長波段，膜面反射率之變 動為未滿2%之範圍内（於橫跨波長365nm〜450ΠΠ1之波長波 段膜面反射率之變動為未滿1%之範圍内）。 以掃描式電子顯微鏡（SEM)，觀察光阻劑圖案、光罩 圖案之雙方，圖案邊緣之凹凸（所謂鋸齒）與實施例丨同樣 地為未滿〇. 1 // m而良好。 (實施例5) 於上述實施例1，將光阻劑膜之膜厚以40()nm〜800nm 之複數膜厚形成光阻劑膜以外，與實施例丨同樣地，形成 光阻劑圖案，製作FPD用大型光罩。 以掃描式電子顯微鏡（SEM)，觀察光阻劑圖案、光罩 圖案之雙方，圖案邊緣之凹凸（所謂鋸齒）與實施例1同樣 地為未滿1 // m而良好。 (比較例） 於大型玻璃基板（合成石英（QZ)10mm厚，尺寸850mmx 1 200mm)上，使用濺鍍裝置，進行遮光性膜之成膜。成膜， 係於2個濺鍍室内配置各個cr靶，首先，以Ar氣體作為 濺鍍氣體將Cr膜（遮光膜）9〇〇埃，接著，以Ar氣體與〇2 2190-8838-PF 21 200809393 氣體作為錢鑛氣體將C r 0膜（反射防止膜）3 〇 〇埃成膜以製 作光罩基底。 結果，於使用於製造FPD用大型光罩時之雷射描緣波 長（例如，365nm、405nm、413nm、436nm、442nm)之雷射 描緣波長波段（350nm〜500nm)，遮光性膜之膜面反射率超 過15%( 18· 3%)。又，包含橫跨上述雷射描繪波長波段之波 長350nm〜45〇ηπι之波長波段，膜面反射率之變動超過 2%(4·2%)。 使用以上述製作之光罩基底，與實施例丨同樣地，於 遮光性膜形成光阻劑膜，於光阻劑膜雷射描繪描繪圖案， 藉由顯影形成光阻劑圖案，將該光阻劑圖案作為掩膜，將 2層構造之膜（Cr膜、CrO膜）一體以濕式蝕刻圖案化，製 作具有寬的通常的圖案咖及^寬的灰階圖案（由 大型FPD用曝光機的解析極限以下之細微遮光圖案及細微 透光部所構成之圖案）12a之FPD用大型光罩。 於上述步驟’以掃描式電子顯微鏡(sem)，對光阻劑All of the photomasks include, for example, a photomask that forms a TFT (thin film transistor), particularly a TFT channel portion or a contact hole portion, a low temperature polycrystalline stone, a color light film, a reflection plate (black matrix), and the like. Other photomasks for display device manufacturing include all photomasks required for the manufacture of organic EL (electroluminescence) displays, plasma displays, and the like. A photomask for manufacturing the FPD device of the present invention, characterized in that: using the photomask substrate for manufacturing the Fpd device of the present invention described above, laser-forming the photoresist formed on the photomask substrate to form a photoresist pattern This mask pattern is used as a mask to form a mask pattern composed of a light-shielding film pattern, and is manufactured (construction 6). Hereinafter, the present invention will be described in more detail based on examples. (Example 1) A large-sized glass substrate (synthesized quartz (QZ) 10 mm thick, size 850 mm x 2190-8838-PF 17 200809393 1 200 mm) was subjected to a large-scale in-line sputtering apparatus, and a crystallizing control layer was provided to have a shading function. Film formation of a lower layer portion and a light-shielding film having a layer portion above the reflection preventing function. The film formation is performed in each of the spaces (sputtering chambers) in which the substrate transfer direction is continuously arranged in a large in-line type sputtering apparatus. First, the CrN layer is formed by using Ar gas and N2 gas as the (four) gas (as a control. The film is crystallized for the purpose of 1 μ Å, and then the Ar gas and CL gas are used as the sputtering gas to form the CrC layer (having a layer under the shading function) of 650 angstroms, followed by Ar gas and (10) gas | The plating gas was formed by continuously forming a CrON layer (having a layer on the upper side of the reflection preventing function) of 25 Å to form a reticle base. Further, each of the films is a composition of a tilting film. Further, the CrC layer (having a layer under the light-shielding function) contains n (nitrogen) due to the gas or N0 gas used in forming the film crN layer or the CrON layer (having a layer for preventing the upper function of the reflection preventing function), so The crN layer, the CrC layer (having a layer under the shading function), and the NCrON layer (having a layer above the reflection preventing function) all contain Cr and N. The spectral reflectance line of the above-mentioned mask base is shown in Fig. 1. Further, the spectral reflectance was measured by a spectrophotometer. The spectral reflectance line shown in Fig. 1 is used in the laser drawing wavelength range (350 nm to 5 雷) of the laser drawing wavelength (for example, 365 nm, 405 nm, 4i3 nm, 436 nm, and 442 nm) for manufacturing a large reticle for FPD. Nm), the film surface reflectance of the light-shielding film is 15% or less. Further, the wavelength band of the wavelength range of 350 nm to 450 nm across the wavelength range of the laser drawing is included, and the variation of the reflectance of the film surface is less than 2% (the film surface reflectance in the wavelength band of 365 nm to 450 nm across the wavelength) In the range of less than 未%) 2190-8838-PF 18 200809393, using the mask base prepared as described above, a phenolic laser resist for photoresist drawing is applied using the slit coater shown in FIG. (The photoresist film thickness range: l〇〇〇nffl±l〇0nm), the photoresist film is laser-drawn, the pattern is drawn, the photoresist pattern is formed by development, and the photoresist pattern is used as a mask. The three-layer structure film (CrN layer, CrC layer, and CrON layer) is integrally patterned by wet etching to produce a general pattern t 121 having a width of 5 " m, and a gray P white pattern having a width of 1//m. A large-sized photomask for FpD (see Fig. 4) (a pattern composed of a fine light-shielding pattern and a fine light-transmitting portion below the analysis limit of the exposure machine for a large-sized FPD) 12a. In the above steps, a scanning electron microscope (SEM) is used to observe both the normal pattern and the gray scale pattern on both the photoresist pattern and the mask pattern, and the pattern is viewed as a concave surface of the pattern edge (so-called sawtooth). ) is not good for 0 · 1 / m. The FpD device manufactured using the large-sized photomask of the obtained FPD also showed no halo and was good. (Example 2) In the same manner as in the first embodiment, the CrON layer (the layer having the upper portion of the antireflection function) was formed to have a thickness of 25 Å in an Ar gas and a N0 gas as a sputtering gas. A photoresist pattern is used to make a large mask for F. The spectral reflectance line shown in FIG. 2 is included in the laser scanning wavelength band (365 nm, 365 nm, 4 〇 5 nm, 413 _, 436 nm 442 nm) used for manufacturing a large reticle for FpD. 450 nm), the film surface reflectance of the light-shielding film was 12% or less. In addition, the wavelength range of the wavelength range of 350 nm to 45 〇 nm of the long wavelength band of the laser depicting wave 2190-8838-PF 19 200809393 is included, and the variation of the reflectance of the film surface is in the range of not S 2% (at a wavelength of 365, 45). The variation of the film surface reflectance in the wavelength band of Shaoguan is within the range of less than 1%).彳 Scanning electron microscope (SEM), observing both the photoresist pattern and the mask pattern, the unevenness of the pattern edge (so-called wrong tooth) is not as good as that of the example i. (Example 3) In the above embodiment, the light was formed in the same manner as in Example i except that the CrON layer (the layer having the upper portion of the antireflection function) was formed by using the Ar gas and the N0 gas as the sputtering gas at a thickness of 32 Å. The resist pattern is used to make a large mask for f. The spectral reflectance line shown in FIG. 2 includes a laser drawing wavelength band (365 nm) including a laser drawing wavelength (for example, 365 nm, 4 〇 5 nm, 413 ffe, 436 nm, and 442 nm) for manufacturing a large reticle for FpD. ～45〇nm), the film surface reflectance of the light-shielding film is 11% or less. Further, the wavelength band of the wavelength range of 35 Onm to 45 Onm in the wavelength range of the laser drawing is included, and the variation of the reflectance of the film surface is in the range of less than 2% (the film surface reflection in the wavelength band of 365 nm to 45 〇 nm across the wavelength) The rate of change is within the range of less than 丨G/.). The both of the photoresist pattern and the mask pattern were observed by a scanning electron microscope (SEM), and the unevenness (so-called serration) of the edge of the pattern was as good as that of the example 丨 1 1 m. (Example 4) In the above-described Example 1, the CrON layer (having a layer portion having an antireflection function) was formed by using Ar gas and NO gas as a sputtering gas at a thickness of 2 -8 -8 -8 838-PF 20 200809393 of 2 Å. In the same manner as in Example 1, a photoresist pattern was formed to fabricate a large-sized photomask for FPD. The spectral reflectance line shown in Figure 2, including the laser depicting wavelengths (for example, 365_, 4〇5_, such as m, 436nm, 442nm) of the laser depicting wavelengths used in the fabrication of Fp]) In the wavelength band (365 nm, 45 〇 nm), the film surface reflectance of the light-shielding film was 14% or less. Further, the wavelength band of the wavelength range of 350 nm to 450 nm in the wavelength range of the laser beam is included, and the variation of the reflectance of the film surface is in the range of less than 2% (the variation of the film surface reflectance in the wavelength band of 365 nm to 450 ΠΠ 1 across the wavelength) Within the range of less than 1%). The scanning electron microscope (SEM) was used to observe both the photoresist pattern and the mask pattern, and the unevenness of the pattern edge (so-called sawtooth) was as good as that of the example 丨. 1 // m. (Example 5) A photoresist pattern was formed in the same manner as in Example 将 except that the film thickness of the photoresist film was formed into a photoresist film by a film thickness of 40 () nm to 800 nm in the above-described Example 1. Make a large mask for FPD. The both of the photoresist pattern and the mask pattern were observed by a scanning electron microscope (SEM), and the unevenness (so-called saw tooth) of the pattern edge was as good as that of Example 1 except that it was less than 1 / m. (Comparative Example) A large-sized glass substrate (synthetic quartz (QZ) 10 mm thick, size 850 mm x 1 200 mm) was used to form a light-shielding film by using a sputtering apparatus. For film formation, each cr target is placed in two sputtering chambers. First, a Cr film (light shielding film) is rubbed with Ar gas as a sputtering gas, and then Ar gas and 〇2 2190-8838-PF 21 are used. 200809393 Gas is used as a money mineral gas to form a film base by forming a C r 0 film (reflection preventing film) 3 〇〇. As a result, in the laser scanning wavelength range (350 nm to 500 nm) of the laser scanning wavelength (for example, 365 nm, 405 nm, 413 nm, 436 nm, and 442 nm) for manufacturing a large-sized photomask for FPD, the film surface of the light-shielding film is used. The reflectance exceeds 15% (18.3%). Further, the wavelength band of the wavelength range of 350 nm to 45 〇 ηπ across the wavelength range of the laser drawing is included, and the variation of the reflectance of the film surface exceeds 2% (4.2%). Using the photomask substrate produced as described above, a photoresist film was formed on the light-shielding film, and a pattern was drawn on the photoresist film by laser, and a photoresist pattern was formed by development, and the photoresist was formed. As a mask, a two-layer structure film (Cr film, CrO film) is integrally patterned by wet etching to produce a gray pattern having a wide normal pattern and a wide width (exposure machine for large FPD) A large-sized photomask for FPD having a fine shading pattern and a pattern of fine light-transmitting portions below the limit) 12a. In the above step 'by scanning electron microscope (sem), the photoresist
圖案、光罩圖案之雙方，觀R 靦察通常的圖案、灰階圖案之雙 方’將圖案以平面視>同安 Λ 1 寻之圖案邊緣之凹凸（所謂鋸齒）為超 過 〇· 1 # m(0. 3// m) 〇Both sides of the pattern and the mask pattern, and the two sides of the pattern and the gray pattern are observed. 'The pattern is viewed in a plane> The same as the edge of the pattern (the so-called sawtooth) is more than 〇· 1 # m ( 0. 3// m) 〇
使用所得FPD用大型光罩製 造之FPD裝置發生了顯示 ’惟本發明並非限 ^以上，舉較佳的實施例說明本發明 定於上述實施例者。The FPD device manufactured using a large-sized photomask of the obtained FPD has been shown to have been shown. The present invention is not limited to the above, and preferred embodiments of the present invention are described in the above embodiments.
2190-8838-PF 200809393 【圖式簡單說明】 圖1係以實施例製作之具有反射防止機能之遮光性膜 之分光穿透率之圖。 圖2係以實施例製作之具有反射防止機能之遮光性膜 之分光穿透率之圖。 圖3係說明使用於實施例及比較例之狹縫塗佈裝置之 示意圖。 圖4係說明FPD用大型光罩之形態之圖。 圖5係說明FPD用大型光罩之其他形態之圖。 圖6係說明具有半透光性膜之灰階光罩之圖，（1)係 部分平面圖，（2)係部分剖面圖。 圖7係說明具有解析極限以下的細微遮光圖案之灰階 光罩之圖，（1)係部分平面圖，（2 )係部分剖面圖。 【主要元件符號說明】 1〜遮光部； 2〜穿透部； 3〜灰階部； 3a〜細微遮光圖案； 3b〜細微穿透部； 3a’〜半透光性膜； 10〜透光性基板； 11〜半透光性膜； 12〜遮光性膜。 2190-8838-PF 232190-8838-PF 200809393 BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a graph showing the spectral transmittance of a light-shielding film having a reflection preventing function produced in the examples. Fig. 2 is a graph showing the spectral transmittance of a light-shielding film having a reflection preventing function produced in the examples. Fig. 3 is a schematic view showing the slit coating apparatus used in the examples and the comparative examples. Fig. 4 is a view showing the form of a large reticle for FPD. Fig. 5 is a view showing another form of a large photomask for FPD. Fig. 6 is a view showing a gray scale mask having a semi-translucent film, (1) a partial plan view, and (2) a partial sectional view. Fig. 7 is a view showing a gray scale mask having a fine light-shielding pattern below the resolution limit, (1) a partial plan view, and (2) a partial cross-sectional view. [Description of main components] 1~shield; 2~penetration; 3~gray section; 3a~fine shading pattern; 3b~fine penetration; 3a'~ semi-transmissive film; 10~transparency Substrate; 11 to semi-translucent film; 12 to light-shielding film. 2190-8838-PF 23
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| JP2007124185A JP5004283B2 (en) | 2006-05-15 | 2007-05-09 | FPD device manufacturing mask blank, FPD device manufacturing mask blank design method, and FPD device manufacturing mask manufacturing method |
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| TWI755337B (en) * | 2017-07-14 | 2022-02-11 | 日商Ｈｏｙａ股份有限公司 | Photomask blank, method of manufacturing photomask, and method of manufacturing display device |
| CN109960105B (en) * | 2017-12-26 | 2024-06-18 | Hoya株式会社 | Photomask blank, method for manufacturing photomask, and method for manufacturing display device |
| JP2021004920A (en) * | 2019-06-25 | 2021-01-14 | Hoya株式会社 | Mask blank, method for manufacturing transfer mask and method for manufacturing semiconductor device |
| JP7463183B2 (en) * | 2019-06-26 | 2024-04-08 | Hoya株式会社 | Mask blank, transfer mask, method for manufacturing a transfer mask, and method for manufacturing a semiconductor device |
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| KR970008372A (en) * | 1995-07-31 | 1997-02-24 | 김광호 | Fine Pattern Formation Method of Semiconductor Device |
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| JPH11125896A (en) * | 1997-08-19 | 1999-05-11 | Toppan Printing Co Ltd | Photomask blank and photomask |
| US6899979B1 (en) * | 1998-07-31 | 2005-05-31 | Hoyo Corporation | Photomask blank, photomask, methods of manufacturing the same, and method of forming micropattern |
| KR100484517B1 (en) * | 2000-12-19 | 2005-04-20 | 호야 가부시키가이샤 | Grayton mask and manufacturing method thereof |
| US6605394B2 (en) * | 2001-05-03 | 2003-08-12 | Applied Materials, Inc. | Organic bottom antireflective coating for high performance mask making using optical imaging |
| JP2003195483A (en) * | 2001-12-28 | 2003-07-09 | Hoya Corp | Photomask blank, photomask and method for manufacturing the same |
| KR100472115B1 (en) * | 2002-07-16 | 2005-03-10 | 주식회사 에스앤에스텍 | Blank-mask and its method for manufacturing |
| KR100779956B1 (en) * | 2002-12-03 | 2007-11-28 | 호야 가부시키가이샤 | Photomask blank and manufacturing process of photomask |
| JP4440688B2 (en) * | 2004-03-31 | 2010-03-24 | Ｈｏｙａ株式会社 | Laser drawing apparatus, laser drawing method, and photomask manufacturing method |
| JP4335729B2 (en) * | 2004-03-31 | 2009-09-30 | 信越化学工業株式会社 | Photomask blank and method for adjusting reflectance of photomask blank |
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