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TW200848918A - Photomask blank and photomask - Google Patents

Photomask blank and photomask Download PDF

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Publication number
TW200848918A
TW200848918A TW097110041A TW97110041A TW200848918A TW 200848918 A TW200848918 A TW 200848918A TW 097110041 A TW097110041 A TW 097110041A TW 97110041 A TW97110041 A TW 97110041A TW 200848918 A TW200848918 A TW 200848918A
Authority
TW
Taiwan
Prior art keywords
film
light
semi
nitrogen
substrate
Prior art date
Application number
TW097110041A
Other languages
Chinese (zh)
Other versions
TWI424261B (en
Inventor
Masaru Mitsui
Masao Ushida
Original Assignee
Hoya Corp
Hoya Electronics Malaysia Sendirian Berhad
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Filing date
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Application filed by Hoya Corp, Hoya Electronics Malaysia Sendirian Berhad filed Critical Hoya Corp
Publication of TW200848918A publication Critical patent/TW200848918A/en
Application granted granted Critical
Publication of TWI424261B publication Critical patent/TWI424261B/en

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Classifications

    • 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
    • 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
    • G03F1/26—Phase shift masks [PSM]; PSM blanks; Preparation thereof
    • G03F1/32—Attenuating PSM [att-PSM], e.g. halftone PSM or PSM having semi-transparent phase shift portion; Preparation thereof
    • 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
    • G03F1/46—Antireflective coatings
    • 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
    • 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
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/091—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers characterised by antireflection means or light filtering or absorbing means, e.g. anti-halation, contrast enhancement
    • 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
    • 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
    • H01L21/0276—Photolithographic processes using an anti-reflective coating
    • 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)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Computer Hardware Design (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Architecture (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Structural Engineering (AREA)
  • Preparing Plates And Mask In Photomechanical Process (AREA)

Abstract

A mask blank is for use in manufacturing a flat panel display device and includes a substrate, a light semi-transmitting film made of a material containing tantalum and formed on the substrate, and a light shielding film made of a material containing chromium and nitrogen and formed on the light semi-transmitting film.

Description

200848918 九、發明說明： 【發明所屬之技術領域】 本發明是關於一種光罩基庙另土 $ 徑疋旱丞底及先罩，特別是關於一種 用來製造平面顯示器裝置之光罩其 心亢皁基底及使用此光罩基底製 造出來之光罩等。 【先前技術】 近年來’在用來製造平面顯示器（以下簡稱為fpd)裝置 之大型FPD用光罩的領域中，嘗試使用具有半透光性區域 (所谓灰階部）之灰階％罩來減少光罩數目（可參照月刊FPD I他⑴gence，P.31_35, 1 999年5月（非專利文獻⑴。 在此’灰階光罩如第1 (A)圖所示，在透明基板上，具 有遮光部卜透光部2及作為半透光性區域之灰階部3。灰階 部3可為形成灰階光罩用半透光性膜（半透光性膜w之區 域’具有調整曝光光線之透過量的功能。灰階物成之目 的在於，藉由減少透過該區域之曝光光線透過量來降低曝 光光線之，、、、射里’將與相關區域對應之光阻在顯像後所減 少之膜厚控制為所要的值。 田將大里灰|^白光罩裝載於鏡像投影式或使用鏡片之鏡 片技〜式之大型曝光裝置上來使用時，通過灰階部3之曝光 光線整體而言曝光量顯得不^，所以，透過此灰階部3曝光 =正性光阻僅僅因為膜厚變薄而殘留在基板上。亦即，如 第1(B)圖所不’光阻隨著曝光量之不同，造成與平常之遮 光部1對應的部分Γ和與灰階部3對應的部分3，對顯像液200848918 IX. INSTRUCTIONS: [Technical field of the invention] The present invention relates to a hood-based temple, a soil, a raft, and a hood, and more particularly to a reticle for manufacturing a flat-panel display device. a soap substrate and a photomask manufactured using the photomask substrate. [Prior Art] In recent years, in the field of large-sized FPD masks for manufacturing flat panel displays (hereinafter abbreviated as fpd) devices, attempts have been made to use a gray scale % mask having a semi-translucent region (so-called gray scale portion). Reduce the number of masks (refer to the monthly publication FPD I (1) Gen, P.31_35, May 999 (Non-patent literature (1). Here's the grayscale mask as shown in Figure 1 (A), on a transparent substrate, The light-shielding portion 2 has a light-transmitting portion 2 and a gray-scale portion 3 as a semi-transmissive region. The gray-scale portion 3 may be a semi-transmissive film for forming a gray-scale mask (the area of the semi-transmissive film w has an adjustment) The function of exposing the amount of light transmitted. The purpose of the gray scale object is to reduce the exposure light by reducing the amount of exposure light transmitted through the region, and to shoot the photoresist corresponding to the relevant region in the image. The film thickness after the reduction is controlled to a desired value. When the field is mounted on a mirror projection type or a large exposure apparatus using a lens lens, the exposure light of the gray scale portion 3 is used as a whole. In fact, the exposure does not appear to be ^, so, through this gray Part 3 Exposure = Positive Photoresist Residue remains on the substrate only because the film thickness is thin. That is, as shown in Figure 1(B), the photoresist does not correspond to the usual light-shielding portion 1 depending on the amount of exposure. Part of the Γ and the part 3 corresponding to the gray scale part 3, the pair of imaging liquid

2130-9519-PF 200848918 之溶解性的差異。因此，顯像後之光阻形狀在與平常之遮 光部1對應的部分γ約為1 # m，在與灰階部3對應的部分 3’約為0.4〜0.5# m，在與透光部2對應的部分則為沒有光 阻的部分2’。之後，在沒有光阻的部分2，上進行被加工 基板的第-钱刻步驟，接著藉由灰化處王里等去除與灰階部3 對應的部分3 ±較薄的光阻，並在此部分進行第二姓刻步 驟。藉此，可以一片光罩進行過去需要兩片光罩的製程’ 減少光罩數目。 關於FPD用之大型光罩基底及大型光罩，有人提出在遮 光性膜下方形成半透光性膜之半透光性膜下置型（半透光 性膜預先附加型）之灰階光罩基底及光罩。 在此半透光性膜下置型之灰階光罩基底及光罩中，在 半透光性膜之材料方面，有人提出石夕化组、氧化艇、氮化 组或從這些材料之混合物中所選取出之材料，在遮光性膜 之材料方面，有人提出鉻（cr)薄膜（可參照特開 20 02-1 96473號公報（專利文獻丨））。 【發明内容】 不k田使用乾韻刻步驟從由上述透光性基板、半透 光性膜（TaSi, Ta〇，TaN)、遮光性膜（Cr)之薄膜構造所缸 成的光罩基底製作光罩日夺，如專利文獻】之實施例所記载， 需要在组系半透光性膜和鉻薄膜之間有S i 0 2之類的钮刻抑 制層，於是出現了薄膜構造變複雜的第i課題。The difference in solubility of 2130-9519-PF 200848918. Therefore, the shape of the photoresist after development is about 1 #m in the portion γ corresponding to the usual light-shielding portion 1, and the portion 3' corresponding to the gray-scale portion 3 is about 0.4 to 0.5 #m, in the light-transmitting portion. The corresponding part of 2 is the part 2' without photoresist. Thereafter, in the portion 2 where there is no photoresist, the first etching step of the substrate to be processed is performed, and then the portion of the substrate corresponding to the gray scale portion 3 is removed by the ashing place, etc., and the thinner photoresist is This section performs the second surname step. Thereby, a process in which two masks are required in the past can be performed by one mask to reduce the number of masks. Regarding the large-sized mask base and the large-sized photomask for FPD, a gray-scale mask base having a semi-transmissive film under-type (translucent film pre-attached type) formed under the light-shielding film has been proposed. And a reticle. In the gray-scale reticle base and the reticle of the semi-transmissive film, in the material of the semi-transmissive film, a Shi Xihua group, an oxidation boat, a nitride group or a mixture of these materials is proposed. For the material to be taken out, a chromium (cr) film has been proposed for the material of the light-shielding film (refer to Japanese Laid-Open Patent Publication No. 20 02-1 96473 (Patent Document No.)). SUMMARY OF THE INVENTION A mask base formed by a film structure of the above-mentioned light-transmitting substrate, semi-transmissive film (TaSi, Ta〇, TaN), and light-shielding film (Cr) is used in the process of dry etching. In the case of producing a reticle, as described in the examples of the patent document, it is necessary to have a button-inhibiting layer such as S i 0 2 between the semi-translucent film and the chrome film, and thus a film structure change occurs. The complex i-th problem.

又，右欲製造的是FPD用大型光罩，當形成光罩圖樣後 2130-9519-PF 200848918 二虫刻步驟時，乾餘刻裝置的規模非常大，出現 了必須引進非常高價位裝置的第2課題。 因此，本發明團隊嘗試使用澄餘刻步驟從由透光性美 板、+透純膜（TaSl，域TaN)、遮光性膜⑽之薄膜 光罩基底來製作光罩。最後，當使用絡踏 液對絡賴進行溼姓刻步驟時，會對在旦系半透光性膜之表 面造成損害，此時發現有難以控制半透光性膜之透過率^ 弟1課題。於是，若要使用㈣刻步驟從由透光性基板、 半透光《(⑽，TaQ，TaN)、遮光性膜⑹之薄膜構造 所組成的光罩基底製作光罩’在實用上，需要在组系半透 先㈣和絡薄膜之間有S102之類的银刻抑制層，於是發現 有薄膜構造變複雜的第1，課題。 另一方面，若不使用组系半透光性膜而使用石夕化姻之 乳化物、石夕化錮之氮氧化物之半透光性膜，石夕化翻之氧化 ，、石夕化銦之氮氧化物之半透光性膜對鉻㈣液的耐性 南，所以，上述第1，課題及第2課題雖^肖除了，但發現 產生了第3課題。例如，若使用灰階光罩用之半透光性膜， 可长得在秩跨!線至g線之波長頻寬中透過率變化對比於 波長變化小（亦即，在橫跨i線至忌線之波長減中具有平面 为光特性）’但發現在這一點上石夕化顧之氧化物、石夕化銦之 氮氧化物的半透光性膜有改善的餘地。 本發明之目的在提供一種可解決上述課題之光罩基底 及光罩。 在專〜進仃達成上述目的之研究之後，發現基板、由In addition, the right to make a large mask for FPD, when the 2130-9519-PF 200848918 second insect engraving step after the formation of the reticle pattern, the size of the dry-removal device is very large, and the first thing that must introduce a very high-priced device appears. 2 topics. Therefore, the inventors of the present invention attempted to fabricate a photomask from a film mask substrate of a translucent plate, a +transparent film (TaS1, a field TaN), and a light-shielding film (10) using a stenciling step. Finally, when the wet-step process is performed on the surface of the semi-translucent film by the use of the complexing solution, it is found that it is difficult to control the transmittance of the semi-transmissive film. . Therefore, in order to use the (four) engraving step, a photomask is formed from a photomask substrate composed of a light-transmissive substrate, a semi-transparent film structure of ((10), TaQ, TaN), and a light-shielding film (6). There is a silver-stained suppression layer such as S102 between the semi-transparent (four) and the entangled film, and the first problem of the film structure is complicated. On the other hand, if the semi-translucent film of the group is not used, the emulsion of Shi Xihuan and the semi-transparent film of the nitrogen oxide of Shi Xihua, the oxidation of Shi Xihua, and Shi Xihua Since the semi-transmissive film of indium oxynitride has a south resistance to chromium (tetra) liquid, the first problem, the second problem, and the second problem are found, but a third problem has been found. For example, if a semi-transmissive film for a gray scale mask is used, the change in transmittance in the wavelength bandwidth of the rank span! line to the g line can be made smaller than the wavelength change (that is, across the i-line to In the case where the wavelength of the line is reduced, the plane has a light characteristic), but it has been found that there is room for improvement in the semi-transmissive film of the oxynitride of the cerium oxide and the oxynitride of the indium. SUMMARY OF THE INVENTION An object of the present invention is to provide a mask base and a mask which can solve the above problems. After the research of the above purpose was achieved,

2130-9519-PF 7 200848918 含有组之材料所構成的半透光性膜、由含〆 所構成的遮光性膜的薄膜 虱之材料 膜在鉻中含有氮構造。根據此薄膜構造，遮光性 速率快速。因此，當使用 /的滢蝕刻 材料的材料所構成… 對由含有上述鉻和氮之 tfM _膜進行渔㈣時，可極力^ 對下層之-系半透光性膜的損傷，並力抑制 抑制層的情況下製造出薄 在不品要蝕刻 码/辱腰構造早純的FPD#罟。 另外發現’當使用鉻蝕刻液對 料的材料所構成的、舟I ^ 3有上述鉻和氮之材 下層之㈣==行"刻時，可極力抑制對 膜之透過率之變可極力抑制半透光性 本發明具有《下之構造。'心制丰透先性膜之透過率。 (第1構造） 一種光罩基底，其為用來 特徵在於包括·· 衣皇之先罩基底，其 基板； 半透光性膜，Λ 所構成；及 由§有在上述基板上所形成之叙的材料 遮光性膜，由人 氮的材料所構成。透光性膜上所形成之鉻和 (第2構造） 如第1構造之弁 料的材料所構罩基底/其中’由含有上述鉻和氮之材 鉻和氮。 '遮光性膜具有複數層構造，各層中含有 2130-9519-Pp 200848918 (弟3構造） 針由：第】或第2構造之光罩基底，复中- 對由含有上述鉻和氫之材 ^ ’當使用絡钱刻液 溼蝕刻時，為抑制對由在下層八/所構成的遮光性膜進行 光性膜的損傷，由含有上述二材料所構成的半透 遮光性膜為鉻中含有氮的薄膜。 材料的材料所構成的 (第4構造） 彳、 如弟1至第3構造中飪姐斗 有上述…料所構成=:::基底…，由含 含麵之材料、含-和氮之材 、-所構成之材料、 石夕之材料中任-種材料所構成。 氧之材料、含叙和 C弟5構造） 喱用來製造FPD裝置之光罩 請專利第i至第4構造中任—構^之在於：使用如申 ,^ 筹仏之先罩基底來製造。 本發明可提供一種光罩基底，♦ 有上述鉻和氮之材料的材料㈣ π虫刻，夜對由含 砗H ㈣㈣成㈣綠膜進行溼蝕列 ”可極力抑制對由在下層含有叙之材？ :::損傷’並且’可在不需要㈣抑制層的二:: 出/專膜構造單純的FPD裝置。 、 ::明了提供-種光罩’其可用來製造極力抑制 了L糸+透光性膜圖樣之損害的FpD裝置。 【實施方式】 以下詳細說明本發明。2130-9519-PF 7 200848918 A semi-translucent film composed of a material containing a group, and a film of a film comprising a light-shielding film made of ruthenium. The film contains a nitrogen structure in chromium. According to this film construction, the light blocking rate is fast. Therefore, when the material of the 滢 etching material is used... When the tfM _ film containing the above chromium and nitrogen is used for fishing (4), the damage of the lower layer-translucent film can be strongly suppressed, and the suppression can be suppressed. In the case of the layer, FPD#罟 which is thin and not pure in the etch code/short-back structure is manufactured. In addition, it was found that when the material of the chromium etching solution is used, the boat I ^ 3 has the above-mentioned chromium and nitrogen materials (four) == line " when it is engraved, the transmittance of the film can be suppressed as much as possible. Inhibition of semi-transparency The present invention has the following construction. 'The heart rate is the permeability of the first film. (1st configuration) A reticle substrate which is characterized in that it comprises a substrate of a cloak, a substrate thereof, a semi-transmissive film, Λ, and § formed on the substrate The material of the material is composed of a material of human nitrogen. The chromium formed on the light transmissive film and the (second structure) material as the material of the first structure are covered by the substrate/in which the chromium and nitrogen are contained from the above-mentioned chromium and nitrogen. 'The light-shielding film has a multi-layer structure, and each layer contains 2130-9519-Pp 200848918 (different 3 structure) needle consists of: the reticle base of the first or second structure, the complex - the material containing the above chromium and hydrogen ^ 'When the wet etching is performed using the entangled liquid, the semi-transmissive light-shielding film composed of the above two materials is contained in the chromium to suppress the damage to the light-shielding film composed of the lower layer/the light-shielding film. Film. The material of the material (the fourth structure) 彳, such as the brothers 1 to 3, the sisters of the above-mentioned materials are composed of the above materials: =::: base..., materials containing the surface, materials containing - and nitrogen - The material formed, and the material of Shi Xizhi are composed of any material. Oxygen material, containing yue and C brother 5 structure) Glue used to make the FPD device mask. Please use the i- to 4th structure of the patent to build it: use the hood base to be manufactured. . The invention can provide a reticle substrate, ♦ a material having the above-mentioned materials of chromium and nitrogen (4) π insect engraving, and a wet etching sequence of a green film containing 砗H (tetra)(tetra)(4) into the night can be strongly suppressed by the lower layer. Material? ::: Damage' and 'can be used without (4) Suppression Layer 2:: Out/Special Membrane Construction Simple FPD Device., :: Clearly Provided - Kind of Photomask' It can be used to manufacture and suppress L糸+ FpD device which is damaged by a translucent film pattern. [Embodiment] Hereinafter, the present invention will be described in detail.

2130-9519-PF 200848918 本發明之用來製造FPI)裝置之 製造FPD裝置之先罩基底及光罩為用來 置之先罩基底，其特徵在於包括： 暴板， 半透光性膜，由令右 所構成；及 基板上所形成之鈕的材料 遮光性膜，由冬女士、 氮的材料所構成（第！構造）。述+透先性膜上所形成之鉻和 根據上述第1構造之本發明， 遮光性膜被鉻钱刻液m幻、“ B口中3有鼠， 处t ,、 的，整蝕刻速率相當快。因此，告#用 念蝕刻液對由含有鉻和 田 ㈣時，可極力抑材料的遮光性膜進行澄 卩制對下層之鈕系半透明性膜之損害，並 了在不茜要Ί虫刻抑制声的# 的FPD裝置。 卩㈣的情況下製造出薄膜構造單純 又’當使用鉻餘刻液對由冬 遮光性膜進行和氮之材料所構成的 性膜之損人 極力抑制對下層之"、半透明 化、於 可極力抑制半透光性膜之透過率之變 化’於是，^於控財透光性膜之透料。 明中’由含有絡和氮之材料所構成的遮光性膜 為在鉻(Cr)中單獨含有氮(N)的型態(CrN)之外，也 可為對鉻⑹和氮（N)加人氧⑻、碳⑹、氫晴元^ 又，藉由由含有鉻和氮之材料所構成的遮光 Μ、⑽、⑽），可使_刻速率比鉻還大，所以效果2130-9519-PF 200848918 The hood substrate and the reticle for manufacturing the FPD device for manufacturing the FPI device of the present invention are used as a hood substrate, and are characterized in that: a blasting plate, a semi-transmissive film, The light-shielding film of the button formed on the substrate and the button formed on the substrate is composed of a material of Ms. Winter and nitrogen (the structure!). The chromium formed on the transparent film and the invention according to the first configuration described above, the light-shielding film is etched by the chrome engraving liquid, and "the mouse has a rat in the B port, and the etch rate is relatively fast." Therefore, the use of the etching solution for the opaque film containing the chrome and the field (four) can be used to reduce the damage of the underlying layer of the translucent film, and it is not necessary to insect the insects. The FPD device that suppresses the sound #. In the case of 卩(4), the film structure is simply created, and when the chromium film is used, the damage caused by the film made of the winter light-shielding film and the nitrogen material is suppressed to the lower layer. ", translucent, can suppress the change of the transmittance of the semi-transparent film as much as possible.] Therefore, it is used to control the transparency of the translucent film. The film is a type (CrN) containing nitrogen (N) alone in chromium (Cr), and may also be added to human (0), carbon (6), and hydrogen (+) to chromium (6) and nitrogen (N). The shading enamel, (10), (10), which consists of a material containing chromium and nitrogen, can make the etch rate higher than that of chromium, so the effect is

2130-9519-PF 10 200848918 較好。又，相較MCr0N，CrN薄膜中不人一 速率變大，於是效果更好。 S虱，所以，溼蝕刻 在本！X明中，上述遮光性膜宜為 圖樣的薄膜。 g由溼蝕刻步驟·製作 在本fx明中，由含組之材料所構成 樣化可使用溼蝕刻或乾蝕刻來進行+性膜的圖 重視成本面及產能的觀點來看 2 ’如上所述，從 在本發明中，由含有二猎由漫钕刻來進行。 的薄膜構造可為由含有鉻和氮舞成的遮光性膜 各層為含有鉻和氮之材料 ：’早層構造或 化）。虽其為複數層構造時，可為 1弟2構 薄膜構造或組成沿著 p s 、、·且成皆不同的積層 … 膜“向連續變化的薄臈構造。 田/、為硬數層構造時，由於各 所構成，或者，由於遮光性膜之膜厚方二有路和氮之材料 略全部區域含有钬$ f ^ 、予方向之全部區域或約 遮光性膜進行㈣刻步驟時，可=對複數層構造之 透光性膜的損害。 了極力抑制對下層之I旦系半 又’當遮光性膜本身或構成 為鉻氧化膜系薄膜(如Cr0薄膜)時，J:二 的=)，使得_彳速率會比路小，所以不宜_ (單芦亦益奴 乳之材枓所構成的遮光性胺 (早層或硬數層構造）宜為在 （尤性膜 數層構造）（第3構造），如此，者使用^的薄膜（單層或複 和氮所椹士、 田使用鉻餘刻液對由含有欽 見所構成之材料的遮光性 S有絡 胰進仃溼蝕刻時，可極力抑制2130-9519-PF 10 200848918 is preferred. Further, compared with MCr0N, the rate of the CrN film is increased, so that the effect is better. S虱, so, wet etching in this! In the above, the light-shielding film is preferably a film of the pattern. g is formed by the wet etching step, and is formed by the material containing the group, and the wet film or the dry etching can be used to carry out the pattern of the + film. The viewpoint of the cost surface and the productivity is as follows. From the present invention, it is carried out by the inclusion of two huntings. The film structure may be a light-shielding film formed by the inclusion of chromium and nitrogen. Each layer is a material containing chromium and nitrogen: 'early layer structure or formation. In the case of a plurality of layers, it is possible to form a thin film structure or a composition that is different in ps, , and from one to the other. The film "contrasts to a continuously changing thin structure. Field / is a hard layer structure. Depending on the composition, or because the film thickness of the light-shielding film and the material of the nitrogen contain a total area of 钬$f^, the entire direction of the direction, or the light-shielding film (four) steps, Damage of the light-transmitting film of the plural layer structure. When the I-density film of the lower layer is suppressed as much as possible, when the light-shielding film itself or a film of a chromium oxide film (such as a Cr0 film), J: two =), The rate of _彳 will be smaller than that of the road, so it is not suitable _ (the light-shielding amine (early layer or hard layer structure) composed of 单 亦 益 奴 奴 宜 宜 宜 宜 宜 早 早 早(3)), in this case, the film using ^ (single layer or complex nitrogen and gentleman, the field using chromium residual engraving for the light-shielding S containing the material composed of Qinzhi has a pancreatic wet etching, Strongly suppress

2130-9519-PF 200848918 對下層之钽系半透光性膜之損害（第3構造）。 在此，當使用絡姓刻液對由含有鉻和氮所構成之材料 =光性膜進行㈣料，若對下層之㈣半透光性膜造 ^貝吾’下層之组系半透光性膜的透過率上升。在本發明 装由紐糸材料所構成的半透純膜於光罩製作的前後（光 基底製作後和光罩製作後），「從超高壓水銀燈放射出來 =橫跨,線至§線之波長頻寬中之透過率之上升量」(以下 :二；述既定之透過率之上升量」)宜㈣以下，為了控 制在^上述既定之透過率之上升量之範圍内’在鉻中含 有氮之遮光性膜（單層或複數層構造）是適宜的選擇。同樣 地’在本發明中，使上述半透光性膜和在對上述遮光性膜 進=圖樣製作時所使用的鉻系材料的姓刻液接觸2分鐘的 :!中從，水銀燈放射出來至少橫跨!線至,線之波長 頻見令之透過率之變化量宜在5%以下。 一又，當上述既定之透過率之上升量超過_，若應 二貫：之光罩製程，將透過率控制在其設定值之(亦 25設定值）這點顯得過於嚴格，又，進行滿足透過率之 口又疋值之±1%的產品製造相當困難。 相對於此，者μ、+、< 士朴 田述既疋之透過率之上升量在5%以下 日·^ ’若應用在實降之古罢希』 之出内很容易'，又，^在其設定值 品製造是實際上辦得到的透 μ值之±1%的產 :的3里且為使上述既定之透過率之變化量為3%以下 的m想上最好為使其為15%以下，甚至幻肩以下2130-9519-PF 200848918 Damage to the lower layer of the semi-translucent film (third structure). Here, when the material consisting of chromium and nitrogen is used to carry out the (four) material, and the semi-transparent layer of the lower layer of the (four) semi-transmissive film is formed. The transmittance of the film increases. In the present invention, a semi-transparent pure film composed of a ruthenium material is produced before and after the reticle is formed (after the production of the light substrate and after the reticle is fabricated), "radiation from the ultrahigh pressure mercury lamp = straddle, the wavelength of the line to the § line The increase in the transmittance of the wide medium (the following: two; the increase in the transmittance of the predetermined transmittance) is preferably (4) or less. In order to control the increase in the transmittance of the above-mentioned predetermined transmittance, 'the nitrogen is contained in the chromium. A light-shielding film (single layer or a plurality of layers) is a suitable choice. Similarly, in the present invention, the semi-transmissive film is exposed to a surname of a chromium-based material used for the production of the light-shielding film in the pattern for 2 minutes: from the mercury lamp, at least Across the line to the line, the wavelength of the line should be seen so that the change in transmittance should be less than 5%. In addition, when the above-mentioned increase in the transmittance exceeds _, if the reticle process is to be repeated: the transmittance is controlled to be at its set value (also set at 25), which is too strict and satisfied. It is quite difficult to manufacture a product with a transmission rate of ±1%. In contrast, the increase in the transmission rate of 朴 田 田 述 田 田 田 在 在 在 在 在 5% 5% 5% ^ 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若In the case where the set value product is manufactured in a range of ±1% of the μ value of the actually obtained μ value, and the amount of change in the predetermined transmittance is 3% or less, it is preferable to make it Less than 15%, even below the shoulder

2130-9519-PF 12 200848918 的含量。 在本發明中，由含有鉻和氮之材 (單層或複數層構造) 遮光性膜 膜，不過…用“ 山夜之座蝕刻速率快速的薄 的·^祕’ 刻液對由含有鉻和氮所構成之材料 ，編膜進行澄㈣時，可極力抑制對下層之：= 明I·生艇之知害，所以為適。 遮光性膜之膜严士一 „ 又，且添加用來提高 速率的^ Γ ㈣域或約略整個區域之^刻 ::::Γ ㈣速率的添加元素可為氮氣等。 —Α;:Γ 由含有絡和氮之材料所構成的遮光性膜 :”、、在::中含有氮的薄膜，以使其對鉻钱刻液之渥钱刻速 率比鉻早體（Cr)之溼蝕刻速率快3倍至2倍。 、 且射又’在本發明中，其宜為在路中含有氮的薄膜，以使 ”對鉻㈣液之㈣刻速率W〜3 W秒之範圍内。 由含有絡和氮之材料所構成的遮光性膜中的氮的含量 最好在15〜6°原子百分比的範圍内。當氮的含量不滿15原子 百分比時’難以得到提高鞋刻速率的效果。X，使上述 既定之透過率之變化量在5%以下將很困難。另一方面，合 氮的含量超過6〇原子百分比時，從超高壓水銀燈放射出； 橫跨i線至g線之波長頻寬中之吸收係數變小。於是，為p 到所要之光學濃度，產生了使膜厚變厚的需要，又由= 刻速率變快，圖樣之剖面形狀惡化，無法使圖樣精度提高， 所以不宜。 又，由含有鉻和氮之材料所構成的㉟光性膜可進一步 含有氧。在此情況下之氧的含量宜比氮的含量少。 2130-9519-PF 13 200848918 在本發明中，由含鈕之材料所構成的半透光性膜宜由 鈕所構成之材料、含鈕之材料、含鈕和氮之材料、含氮和 氧之材料、含鈕和矽之材料中任一種材料所構成（第4構 造）。 具體而言，由含鈕之材料所構成的半透光性膜可為鈕 單體（Ta)、氮化纽（TaN)、氧化组（Ta〇)、氮氧化组（TaN〇)、 含有鈕和矽之材料（TaSi，TaSiN，TaSi〇，TaSi〇N等）、含 f 鈕、矽、硼之材料（TaSiB，TaSiM, TaSiB〇，TaSiB_ 等）、含有鈕和硼之材料（TaB，TaM，TaB〇, TaB⑽等）、含 有鈕和錯之材料（TaGe，TaGeN，TaGe〇, TaGe〇N等）、含有 鈕、鍺、矽之材料（TaGeSiB, TaGeSiBN, TaGeSiB〇2130-9519-PF 12 200848918 content. In the present invention, a light-shielding film made of a material containing chromium and nitrogen (single layer or a plurality of layers) is used, but the "etching rate of the mountain night seat is fast and thin" is used to contain chromium and When the film is made of nitrogen, it can be suppressed to the lower layer as much as possible: = I know the damage of the boat, so it is suitable. The film of the light-shielding film is strict and is added to improve The rate of the ^ 四 (four) domain or approximately the entire area of the ^:::: Γ (four) rate of the added element can be nitrogen and so on. —Α;:Γ A light-shielding film composed of a material containing nitrogen and nitrogen: “, a film containing nitrogen in :: to make the rate of chrome engraving faster than chromium precursor (Cr The wet etching rate is 3 times to 2 times faster. And, in the present invention, it is preferably a film containing nitrogen in the road, so that the rate of (4) to the chromium (tetra) liquid is W~3 W seconds. Within the scope. The content of nitrogen in the light-shielding film composed of the material containing the complex and nitrogen is preferably in the range of 15 to 6 ° atomic percent. When the nitrogen content is less than 15 atom%, it is difficult to obtain an effect of increasing the shoe-cutting rate. X, it will be difficult to make the above-mentioned change in the transmittance below 5%. On the other hand, when the content of nitrogen exceeds 6 〇 atomic percentage, it is emitted from an ultrahigh pressure mercury lamp; the absorption coefficient in the wavelength bandwidth across the i line to the g line becomes small. Therefore, for p to the desired optical density, there is a need to increase the film thickness, and the rate of the engraving becomes faster, and the cross-sectional shape of the pattern is deteriorated, so that the accuracy of the pattern cannot be improved, which is not preferable. Further, the 35-light film composed of a material containing chromium and nitrogen may further contain oxygen. In this case, the oxygen content is preferably less than the nitrogen content. 2130-9519-PF 13 200848918 In the present invention, the semi-translucent film composed of the material containing the button is preferably composed of a button, a material containing a button, a material containing a button and nitrogen, and a nitrogen and oxygen-containing material. The material, the material containing the button and the material of the crucible is composed of (the fourth structure). Specifically, the semi-translucent film composed of the material containing the button may be a button (Ta), a nitride (TaN), an oxidation group (Ta〇), a nitrogen oxide group (TaN〇), and a button. And bismuth materials (TaSi, TaSiN, TaSi〇, TaSi〇N, etc.), materials containing f-button, bismuth, boron (TaSiB, TaSiM, TaSiB〇, TaSiB_, etc.), materials containing buttons and boron (TaB, TaM, TaB〇, TaB(10), etc.), materials containing buttons and faults (TaGe, TaGeN, TaGe〇, TaGe〇N, etc.), materials containing buttons, ruthenium, iridium (TaGeSiB, TaGeSiBN, TaGeSiB〇

TaGeSiBON等）等。 ’ 士又，當使用FPD用大型光罩基底時，若半透光性膜之钱 刻時間變長，半透光性膜圖樣之剖面形狀會惡化，亦即， 形狀幺制性會惡化’結果其成為⑶精度惡化的原因。從加 ==膜之溼崎率的觀點來看，宜在含有上述组 =:::Ta，TaN的材料，又，從加快半透光性膜之乾 、羊的觀點來看，宜在含有上述组 的材料。半透光性膜之膜厚最好為2一 在本發明中，由含有鉻氮 的蝕刻液Λ # 虱之材枓所構成的遮光性膜 為含有确酸錢鈽和過氯酸的钱刻液等。 刻液可為_ ^ / —之材枓所構成的半透光性膜的蝕 」^虱虱化鈉等。TaGeSiBON, etc.). 'When you use a large mask base for FPD, if the time of the semi-transmissive film becomes longer, the cross-sectional shape of the semi-transmissive film pattern will deteriorate, that is, the shape control property will deteriorate. This becomes the cause of (3) deterioration in accuracy. From the viewpoint of the ratio of the wetness of the film to the == film, it is preferable to contain the material of the above group =:::Ta, TaN, and from the viewpoint of accelerating the drying of the semi-transparent film and the sheep, it is preferable to contain The materials of the above group. The film thickness of the semi-translucent film is preferably two. In the present invention, the light-shielding film composed of the etching liquid containing chrome-nitrogen Λ# 虱 is a money engraving containing sulphuric acid and perchloric acid. Liquid, etc. The etchant may be an etched film of a semi-transmissive film composed of _ ^ / -.

2130-9519-PF 14 200848918 在本务明中，由含-之材料 崎體可為氯系氣體或氣系氣體等。 轉 在本發明中，所謂「盥 h 、夺、主榮成社 /、蝕J液接觸」疋指吹氣、喷霧、 貝4使其和各種蝕刻液接觸。 在本發明中，將「 一 攸起尚壓水銀燈放射出來至少橫跨i 線至g線之波長頻官φ 加 透過率」特別視為問題的理由為， ®使用FPD用大型光里日本 單守，利用超南壓水銀燈之i線至g線的 廣大波長頻官，推a夕a 夕色波曝光，同時，從作為曝光光源 起㈣水銀燈放射出鳴、h線、g線的曝光光線強川^ 對強度）幾乎相等，從相舒 、 邳對強度來看，1線、h線、g線必須 看成是同等重要（參照第3圖）。 在本發明中，例示㈣高屢水銀燈可為具有第3圖所示 之特性的水銀燈，不過本發明本身不受此限定。 在本《月中I板可為合成石英、納舞玻璃、無驗玻 璃等對曝光光線具有透光性的基板等。 在本發明中，用來製造FPD裝置之光罩基底及光罩可為 用來製造LCD(液晶顯示器）、電漿顯示器、有機 EL(electr〇luminescence)顯示器等FpD裝置的光罩基底及 光罩等。 在此，LCD製造用光罩包含製造lCD時所需要之所有光 罩例如，TFT(薄膜電晶體），其尤其包含用來形成TFT通 迢部或接觸洞部位、低溫多晶矽TFT、彩色濾光片、反射板 (超黑矩陣）等的光罩。其他的顯示裝置製造用光罩包含製 造有機EL(electroluminescence)顯示器、電漿顯示器等時2130-9519-PF 14 200848918 In the present invention, the material containing - can be a chlorine-based gas or a gas-based gas. In the present invention, the so-called "盥 h , 夺 , 主荣成社 /, JJ liquid contact" means blowing, spraying, and shelling 4 to make contact with various etching liquids. In the present invention, the reason why the "wavelength frequency φ plus the transmittance of at least the i-line to the g-line emitted from the mercury lamp is raised" is considered as a problem, and the use of the FPD for large-scale light in Japan is used. Using the wide-wavelength frequency of the super-Southern pressure mercury lamp from the i-line to the g-line, push the a-day ray wave exposure, and at the same time, from the exposure light source (4) the mercury lamp emits the sound, the h-line, the g-line exposure light. The intensity is almost equal. From the point of view of the strength of the phase and the enthalpy, the 1 line, the h line, and the g line must be regarded as equally important (see Fig. 3). In the present invention, the (IV) high-mercury mercury lamp can be exemplified as a mercury lamp having the characteristics shown in Fig. 3, but the present invention is not limited thereto. In the middle of the month, the I plate may be a substrate that is translucent to the exposure light, such as synthetic quartz, nano dance glass, and non-test glass. In the present invention, the reticle base and the reticle for manufacturing the FPD device may be a reticle substrate and a reticle for manufacturing an FpD device such as an LCD (Liquid Crystal Display), a plasma display, an organic EL (electr luminescence) display or the like. Wait. Here, the reticle for LCD manufacturing includes all of the reticle required for manufacturing the CD, for example, a TFT (Thin Film Transistor), which particularly includes a TFT for forming a via or a contact hole portion, a low temperature polysilicon TFT, and a color filter. A mask such as a reflector (super black matrix). Other photomasks for manufacturing display devices include when an organic EL (electroluminescence) display, a plasma display, etc. are manufactured.

2130-9519-PF 15 200848918 所需要的所有光罩。 本發明之用來製造fpdf 罢 L ^ , 衣置之先罩的特徵為，使用製造 上述本發明之FPD裝置 ^ 置的先罩基底來製造（第5構造）。 關於本發明之用來势 罢苴产L 〇、 木^FPD叙置之光罩的製造為，在光 罩基底上形成之遮光付趙 身 、上糟由湮蝕刻進行圖樣製作，在 半透光性膜上藉由溼飯刿七έ 、 刻或乾蝕刻進行圖樣製作，形成遮 光性膜圖樣及半透光性膜圖樣。 ί 以下使用第2圖來說明傕用束洁止#时 凡乃彳史用牛透光性膜下置型之fpd用 大型光罩基底製造半透^ -表t牛透先性下置型之灰階光罩的製程的其 中一例0 “先I行依_人在透光性基板1 6表面形成半透光性膜 1 7、遮光性膜丨8的製程，形成光罩基底2〇，作為準備（第2(八） 圖）。 在此半透光性膜17可藉由使用金屬Ta、由含有Ta、 S ί之材料等所構成之濺鍍靶材的濺鍍成膜來形成。其膜厚 根據所需要之半透光性膜之透過率（例如2〇〜6〇%)作適當選 定0 又’遮光性膜1 8可藉由使用氮、氧、甲烷、二氧化碳、 一氧化氮、碳酸氣體、碳化氫系氣體或這些混合氣體等之 反應性氣體的反應性濺鍍技術，使用由金屬Cr所構成之濺 鐘無材形成一層或多層構造的薄膜（例如附有反射防止薄 膜之遮光性膜）。 在形成多層構造之遮光性膜18的情況下，可從透明基 板那側依序由氮化鉻薄膜 '碳氮化鉻薄膜、氮氧化鉻薄膜2130-9519-PF 15 200848918 All masks required. The first cover for manufacturing the fpdf of the present invention is characterized in that it is manufactured using the cover substrate of the above-described FPD apparatus of the present invention (the fifth structure). The reticle of the present invention for the production of L 〇, wood FP FPD is made up of a shading body formed on the reticle base, and the smear is etched to form a pattern, and is semi-transparent. The film is formed by wet rice enamel, engraving or dry etching to form a light-shielding film pattern and a semi-transmissive film pattern. ί The following figure 2 is used to illustrate the use of 洁 洁 止 # 时 时 时 时 时 时 时 时 时 时 时 时 时 透光 透光 透光 透光 透光 透光 透光 透光 透光 透光 透光 透光 透光 透光 透光 透光 透光 透光 透光 透光 透光 透光 透光 透光 透光 透光 透光 透光 透光 透光One example of the process of the cover is 0. The process of forming the semi-transmissive film 17 and the light-shielding film 8 on the surface of the light-transmitting substrate 16 is performed in the first row. 2 (8) Fig.) The semi-transmissive film 17 can be formed by sputtering using a metal Ta, a sputtering target composed of a material containing Ta or S ί, etc. The transmittance of the semi-transmissive film required (for example, 2 〇 to 6 〇%) is appropriately selected as 0. The opaque film 18 can be made by using nitrogen, oxygen, methane, carbon dioxide, nitrogen monoxide, carbonic acid gas, In the reactive sputtering technique of a hydrocarbon gas or a reactive gas such as a mixed gas, a film having one or more layers (for example, a light-shielding film with an antireflection film) formed of a sputtering ring made of metal Cr is used. In the case of forming the light-shielding film 18 of a multilayer structure, it can be sequentially from the side of the transparent substrate Chromium nitride film 'Chromium carbonitride film, chromium oxynitride film

2130-9519-PF 16 200848918 之材料構成。此時，遮光性 人 臈之膑；方向之約略整體區域 δ鉻及氮，或者，進一步右久 但一 乂在各層中含有更多氮，藉此，可 徒南進行溼蝕刻時之溼蝕刻速率。 μ ^ 手又虱化鉻膜由以氮化 鉻（CrN)為主成份的一層，可 ^ j具有例如10〜2〇nm的膜厚。碳 见化絡膜為以碳氮化鉻（CrCN)為主成份的—層，可且有例 如25，nm的膜厚。氮氧化鉻膜為以氮氧化鉻（⑽）為主成 份的一層，在功能上作為反射防止層，可具有例如15〜3〇咖 的膜厚。2130-9519-PF 16 200848918 Material composition. At this time, the shading is awkward; the direction is about the entire area δ chrome and nitrogen, or, further, the right is long but the yttrium contains more nitrogen in each layer, thereby allowing the wet etching rate when wet etching . The μ ^ hand chrome film is composed of a layer containing chromium nitride (CrN) as a main component, and has a film thickness of, for example, 10 to 2 〇 nm. The carbonized film is a layer mainly composed of chromium carbonitride (CrCN), and may have a film thickness of, for example, 25 nm. The chromium oxynitride film is a layer mainly composed of chromium oxynitride ((10)), and functionally functions as an antireflection layer, and may have a film thickness of, for example, 15 to 3 Å.

又，遮光性膜18在灰階光罩30的製程中，對由含鈕之 材料所構成的半透光性膜的蝕刻液或蝕刻氣體具有耐性。 接著，在上述光罩基底2〇的遮光性膜18上，形成光阻 薄膜（正性光阻薄膜、負性光阻薄膜等），使用電子線或雷 射掃描裝置曝光此光阻薄膜，藉由光阻之顯像液使之顯 像，形成第一光阻圖樣21 (第2(B)圖）。此第一光阻圖樣21 形成將所製造之灰階光罩3〇之透光部14(第2(H)圖）作為開 口區域的形狀。又，形成第一光阻圖樣21的光阻可使用酚 酸系光阻。 將已形成第一光阻圖樣21的光罩基底20浸潰於鉻蝕刻 液中，使用此鉻蝕刻液體並將第一光阻圖樣21作為光罩， 對光罩基底2 0之遮光性膜18進行溼钱刻步驟（第2 (c )圖）。 藉由此溼蝕刻步驟，在遮光性膜18上形成遮光性膜圖樣22。 形成上述遮光性膜圖樣22之後，使用光阻剝離液剝離 在此遮光性膜圖樣22上所殘留的第一光阻圖樣21 (第2(D) 圖）〇 2130-9519-PF 17 200848918 …接著，將遮光性膜圖樣22作為光罩，對半透光性膜17 '行& v驟或u刻步驟’形成半透光性膜圖樣2 3 (第 2(E)圖）。藉由這些遮光性膜圖樣以及半透光性膜圖樣μ， 形成透光部14。Further, the light-shielding film 18 is resistant to an etching liquid or an etching gas of the semi-transmissive film composed of the material of the button in the process of the gray scale mask 30. Next, a photoresist film (positive photoresist film, negative photoresist film, etc.) is formed on the light-shielding film 18 of the mask substrate 2, and the photoresist film is exposed by an electron beam or a laser scanning device. It is visualized by a developing solution of a photoresist to form a first photoresist pattern 21 (Fig. 2(B)). The first photoresist pattern 21 has a shape in which the light-transmitting portion 14 (second (H) map) of the manufactured gray scale mask 3 is formed as an opening region. Further, a phenolic photoresist can be used as the photoresist for forming the first photoresist pattern 21. The mask substrate 20 on which the first photoresist pattern 21 has been formed is immersed in a chrome etching solution, and the chrome etching liquid is used and the first photoresist pattern 21 is used as a mask to the light-shielding film 18 of the mask substrate 20. Carry out the wet money engraving step (Fig. 2(c)). The light-shielding film pattern 22 is formed on the light-shielding film 18 by this wet etching process. After the light-shielding film pattern 22 is formed, the first photoresist pattern 21 remaining on the light-shielding film pattern 22 is peeled off using a photoresist stripping solution (Fig. 2(D)) 〇 2130-9519-PF 17 200848918 ... The light-shielding film pattern 22 is used as a mask, and the semi-transmissive film 17 is subjected to a semi-transmissive film pattern 2 3 (Fig. 2(E)). The light-transmitting portion 14 is formed by these light-shielding film patterns and the semi-transmissive film pattern μ.

>如上所述，形成半透光性膜圖樣23之後，針對構成遮 光性膜圖樣22的遮光性膜18，進行去除所要部分以外的製 程。亦即，在遮光性膜圖樣22及透光性基板16上形成光阻 =膜，以和前述相同的方式曝光、顯像此光阻薄膜，形成 第_光阻圖樣24(第2⑺圖）。此第二光阻圖樣Μ形成將灰 階部15作為開口區域的形狀。接著，將第二光阻圖樣μ作 為光罩，使用上述鉻蝕刻液對構成遮光性膜圖樣U的遮光 性膜18進一步進行溼蝕刻步驟（第2(G)圖）。 之後，使用光阻剝離液剝離殘留的第二光阻圖樣％。 最後’得到灰階光罩3〇, #具有遮光部13,肖遮光部13為 由半透光性膜17所構成的灰階部15、遮光性膜18及半透光 性膜17的積層（第2(H)圖）。 又，在第2圖所示之半透光性膜下置型（先裝載）之灰階 f罩的製程中，半透光性膜17包含遮光性膜18的重疊蝕刻 時間，和鉻蝕刻液接觸的時間最長合計約為2分鐘。 以下將根據實施例進一步詳細說明本發明。 (第1實施例） (光罩基底之製作） 基板使用了大型玻璃基板（合成石英（QZ)，厚度1〇_，> After the semi-transmissive film pattern 23 is formed as described above, the light-shielding film 18 constituting the light-shielding film pattern 22 is subjected to a process other than the desired portion. That is, a photoresist = film is formed on the light-shielding film pattern 22 and the light-transmitting substrate 16, and the photoresist film is exposed and developed in the same manner as described above to form a first photoresist pattern 24 (Fig. 2 (7)). This second photoresist pattern Μ forms a shape in which the gray scale portion 15 is an open region. Next, the second photoresist pattern μ is used as a photomask, and the light-shielding film 18 constituting the light-shielding film pattern U is further subjected to a wet etching step (second (G) diagram) using the above-described chromium etching solution. Thereafter, the remaining second photoresist pattern % was peeled off using a photoresist stripper. Finally, a gray scale mask 3 is obtained, # has a light-shielding portion 13, and the shading portion 13 is a laminate of a gray scale portion 15 composed of the semi-transmissive film 17, a light-shielding film 18, and a semi-transmissive film 17 ( Figure 2 (H)). Further, in the process of the half-transmissive film under-mounted (first loaded) gray-scale f-cover shown in FIG. 2, the semi-transmissive film 17 includes the overlapping etching time of the light-shielding film 18, and is in contact with the chromium etching solution. The maximum time is about 2 minutes. Hereinafter, the present invention will be described in further detail based on examples. (First Embodiment) (Production of Photomask Base) A large-sized glass substrate (synthetic quartz (QZ), thickness 1 〇 _) was used for the substrate.

大小 850mmxl 200mm)。 2130-9519-PF 18 200848918 在上述基板上，使用大型濺鍍裝置，進行半透光性膜 的薄膜形n體來說’使用絲材’將氬氣作為賤鑛氣 體為使此半透光性膜在i線（365nm)的波長中有的透過 率’形成膜厚4nm的組（Ta)薄膜。 接著，在上述半透光性膜之上，形成由含有鉻和氮之 材料所構成的遮光性膜。具體來說，制絲材，先將氯 氣和氮氣作為濺鍍氣體，形成厚度15_的（：1^薄膜^4〇原 子百刀比）’接著將氬氣、甲院、氮氣作為濺鑛氣體，形成 厚度65nn^CrCN薄膜（N:1〇原子百分比，⑺“原子百分 比）’然》，將氬氣和-氧化氮氣體作為滅鑛氣體，形成厚 度25·的Cr0N薄膜（N:3〇原子百分比’ 〇:3〇原子百分比）， 此連、貝开/成薄膜而成為遮光性膜。又，各層薄膜分別為 組成傾斜膜。 藉由以上的製程，製作FPD用大型光罩基底。 測疋在基板上形成半透光性膜的 g線的波長頻寬的分光透.至八上★ 也、51線至 刀光透過率。分先透過率藉由分光光度計 (曰立製作所社製U-4100)來測定。 (光罩之製作） 光述第2圖所示之半透光性膜下置型之灰 ^广I造光罩。此時，關於由含有鉻和氮之材料所 =光性膜的姓刻液，在常溫下使用含有確酸銨鈽和 :、評：、)虫刻液’接觸時間(姓刻時間)合計在2分鐘以内。 製作光罩之後的灰階部15中的分光透過率藉由分夫Size 850mmxl 200mm). 2130-9519-PF 18 200848918 On the above substrate, using a large-scale sputtering apparatus, a thin film-shaped n-body of a semi-translucent film is used, and argon gas is used as a bismuth gas for the semi-transparent property. The film has a transmittance at a wavelength of i line (365 nm) to form a group (Ta) film having a film thickness of 4 nm. Next, a light-shielding film made of a material containing chromium and nitrogen is formed on the semi-translucent film. Specifically, for the wire-making material, chlorine gas and nitrogen gas are first used as a sputtering gas to form a thickness of 15 _ (: 1 ^ film ^ 4 〇 atomic ratio) 'then argon gas, a hospital, nitrogen as a splashing gas , forming a thickness of 65 nn ^ CrCN film (N: 1 〇 atomic percentage, (7) "atomic percentage" 'Ran", argon gas and - nitrous oxide gas as a mineral gas to form a Cr0N film of thickness 25 (N: 3 〇 atom The percentage '〇: 3〇 atomic percentage), the film is opened and formed into a light-shielding film. Further, each layer of the film is a composition of a tilt film. By the above process, a large mask base for FPD is produced. The wavelength of the g-line of the semi-transmissive film formed on the substrate is divided into light-transmitting light to the upper layer, and the light transmission rate is 51 line to the knives. The first transmittance is measured by a spectrophotometer (manufactured by Kyoritsu Seisakusho Co., Ltd.) -4100) Measured. (Production of Photomask) The ash-wide I hood of the semi-transmissive film under the type shown in Fig. 2 is described. At this time, the material containing chromium and nitrogen = light The name of the film is engraved, and it is used at room temperature to contain ammonium sulphate and: Room (surname engraved time) Total within 2 minutes in the gray portion 15 after forming the mask points by the spectral transmittance Cardiff

2130-9519-PF 19 200848918 : “所社裝U-4_來測定。最後，光罩製作前 ，土底製作後和光罩製作後）的灰階部i 5中橫跨丨線 至g線的波長頻寬的透過率變化量減少為3%以下。此外，所 ^光^作!後的灰階部15中橫跨1線至㈣的波長頻寬的 透過率麵^化量，是指伸用 里疋扣使用形成丰透先性膜17之後所測定之 f. 分光透過率和在製作光罩之後於灰階部15所測定之分光透 過率所算出的值。此點亦在之後所說明的所有範例中適用。 又，在使用電子顯微鏡觀察灰階部丨5的表面（上面）的 表面狀態之後，看不出鉻系薄膜之㈣液之侵料導致的 損害。 再者，在使用電子顯微鏡觀察灰階部15 的表面狀態之後，看不纽系薄膜之_液之侵:=面致 的粗糙表面。 (第2實施例） (光罩基底之製作） 基板使用了大型玻璃基板（合成石英（Qz)，厚度， 大小 850mmxl 200mm)。 在上述基板上，使用大型濺鍍裝置，進行半透光性膜 的薄膜形成。具體來說’使用鈕靶材，將氬氣及氮氣的混 合氣體作為濺鍍氣體，藉由DC磁控反應性濺鍍技術，形成 厚度6_的氮化鈕（TaN)薄膜，以使此半透光性膜在i線 (365ηιη)之波長中的透過率為4〇%。此薄膜組成為7〇原子百 分比的Ta和30原子百分比的n。 接著，在上述半透光性膜之上，形成由含有鉻和氮之2130-9519-PF 19 200848918 : "The U-4_ is measured by the agency. Finally, before the production of the mask, after the production of the soil and after the reticle is made," the gray line i 5 crosses the 丨 line to the g line. The amount of change in the transmittance of the wavelength band is reduced to 3% or less. In addition, the transmittance of the wavelength band across the line width of the gray line portion 15 after the light beam is 15 to 4 is the extension. The value calculated by f. the spectral transmittance measured after the formation of the abundance-precursive film 17 and the spectral transmittance measured in the gray scale portion 15 after the mask is produced is used in the middle of the buckle. This point is also explained later. In addition, in the case of observing the surface state of the surface (upper surface) of the gray-scale portion 丨5 using an electron microscope, damage caused by the contamination of the (four) liquid of the chromium-based film is not observed. After observing the surface state of the gray scale portion 15 by the microscope, it is not possible to invade the surface of the ruthenium film: the rough surface of the surface. (Second embodiment) (Production of the reticle base) The substrate is made of a large glass substrate (synthesis) Quartz (Qz), thickness, size 850mmxl 200mm). On the above substrate, use large splash The plating apparatus performs film formation of a semi-translucent film. Specifically, a button body is used, and a mixed gas of argon gas and nitrogen gas is used as a sputtering gas, and a thickness of 6_ is formed by DC magnetron reactive sputtering technology. a nitride button (TaN) film such that the transmittance of the semi-transmissive film in the wavelength of the i-line (365 ηηη) is 4〇%. The film composition is 7 〇 atomic percent of Ta and 30 atomic percent of n Next, on the semi-transmissive film, formed by containing chromium and nitrogen

2130-9519-PF 20 200848918 材料所構成的遮光性膜。具體來說，使用鉻把材，先將氯 汍矛氮氣作為，賤鍍氣體，形成厚度⑽的Ci薄膜（n : 原 子百刀比）’接著將氬氣、甲烷、氮氣作為濺鍍氣體，形成 厚度65nm的CrCN薄膜（N:10原子百分比，c:1〇原子百分 比），然後，將氬氣和—氧化氮氣體作為錢氣體，形成厚 度25nm的Cr〇N薄膜（N:3〇原子百分比，〇:3〇原子百分比）， 如此連、_形成薄膜而成為遮光性膜。χ，各層薄膜分別為 組成傾斜膜。 f 藉由以上的製程，製作FPD用大型光罩基底。 又，測定在基板上形成半透光性膜的階段中橫跨丨線至 g線的波長頻寬的/分光透過率。分光透過率藉由&光光度計 (曰立製作所社製U-41 0 0)來測定。 (光罩之製作） 接著，根據上述第2圖所示之半透光性膜下置型之灰階 光罩製私製造光罩。此時，關於由含有鉻和氮之材料所構 (成的遮光性膜的蝕刻液，在常溫下使用含有硝酸銨鈽和過 氯酸的蝕刻液，接觸時間（蝕刻時間）合計在2分鐘以内。 (評估） 製作光罩之後的灰階部15中的分光透過率藉由分光光 度計（曰立製作所社製U — U00)來測定。最後，光罩製作前 後（光罩基底製作後和光罩製作後）的灰階部丨5中橫跨i線 至g線的波長頻寬的透過率變化量減少為3%以下。 又，在使用電子顯微鏡觀察灰階部15的表面（上面）的 表面狀心之後，看不出鉻系薄膜之蝕刻液之侵钱所導致的2130-9519-PF 20 200848918 A light-shielding film composed of materials. Specifically, using a chromium material, a chloranium spear nitrogen gas is first used as a ruthenium plating gas to form a thickness (10) of a Ci film (n: atomic ratio), and then argon gas, methane, and nitrogen gas are used as a sputtering gas to form A CrCN film having a thickness of 65 nm (N: 10 atomic percent, c: 1 atomic percent), and then argon gas and nitrogen oxide gas were used as money gas to form a Cr〇N film having a thickness of 25 nm (N: 3 atomic percent by atom, 〇: 3 〇 atomic percentage), so that the film is formed into a light-shielding film. χ, each layer of film is composed of a slanted film. f By the above process, a large mask base for FPD is produced. Further, the spectral transmittance/wavelength transmittance across the ridge line to the g line in the stage of forming the semi-translucent film on the substrate was measured. The spectral transmittance was measured by a & photometer (U-41 0 0 manufactured by Seiko Seisakusho Co., Ltd.). (Production of Photomask) Next, a photomask was produced by the gray-scale photomask of the semi-transmissive film under-type type shown in Fig. 2 described above. In this case, the etching liquid containing the lanthanum nitrate and perchloric acid is used as an etching solution for the light-shielding film formed of a material containing chromium and nitrogen, and the contact time (etching time) is less than 2 minutes in total. (Evaluation) The spectral transmittance in the gray scale portion 15 after the mask was produced was measured by a spectrophotometer (U-U00 manufactured by Seiko Seisakusho Co., Ltd.). Finally, before and after the mask fabrication (after the mask base was fabricated and the mask) The amount of change in transmittance of the wavelength band across the i-line to the g-line in the gray scale portion 丨5 after the production is reduced to 3% or less. Further, the surface of the surface (upper surface) of the gray scale portion 15 is observed using an electron microscope. After the center of the heart, the intrusion of the etchant of the chromium-based film is not seen.

2130-9519-PF 21 200848918 損害。 再者，在使用電子顯微鏡觀察灰階部丨5的剖面（側面） 的表面狀態之後，看不出鉻系薄膜之蝕刻液之侵蝕所導致 的粗糖表面。 (弟3實施例） (光罩基底之製作） 基板使用了大型玻璃基板（合成石英（QZ)，厚度1〇mm， 大小 850_xl 200nm)。 C' 、、 . 在上述基板上，使用大型濺鍍裝置，進行半透光性膜 的薄膜形成。具體來說，使用鈕革巴材，將氮氣及氧氣的混 合氣體作為濺鍍氣體，藉由DC磁控反應性濺鍍技術，形成 厚度12nm的氧化鈕（Ta〇)薄膜，以使此半透光性膜在丄線 ( 365nm)之波長中的透過率為4〇%。此薄膜組成為38原子百 分比的Ta和62原子百分比的〇。 接著，在上述半透光性膜之上，形成由含有鉻和氮之 (材料所構成的遮光性膜。具體來說，使用絡歡材，先將氨 乳和亂氣作為?峻氣體，形成厚度15mn的CrN薄膜（N:40原 子百分比），接著將氬氣、甲烧、氮氣作為滅鍵氣體，形成 厚度65n^〇CrCN薄膜（N:1〇原子百分比，c:i〇原子百分 比）^後，將氬氣和—氧化氮氣體作為㈣氣體，形成厚 度25㈣的⑽薄膜(N:3〇原子百分比，〇:3〇原子百分比）， 如此連續形成薄膜而成為遮光性膜。又，各層薄膜分別為 組成傾斜膜。 藉由以上的製程，製作FPD用大型光罩基底。2130-9519-PF 21 200848918 Damage. Further, after observing the surface state of the cross section (side surface) of the gray-scale portion 丨5 using an electron microscope, the surface of the raw sugar caused by the etching of the etching liquid of the chromium-based film was not observed. (Embodiment 3) (Production of mask base) A large glass substrate (synthetic quartz (QZ), thickness 1 mm, size 850_xl 200 nm) was used for the substrate. C', , . On the above substrate, a thin film of a semi-translucent film was formed using a large sputtering apparatus. Specifically, using a button leather material, a mixed gas of nitrogen gas and oxygen gas is used as a sputtering gas, and a DC magnetron reactive sputtering technique is used to form a thin film (Ta〇) film having a thickness of 12 nm to make the semi-transparent. The transmittance of the photo film in the wavelength of the ruthenium (365 nm) was 4%. This film was composed of 38 atomic percent Ta and 62 atomic percent germanium. Next, on the semi-translucent film, a light-shielding film made of a material containing chromium and nitrogen is formed. Specifically, a honeycomb material is used, and ammonia milk and disorder gas are first formed as a gas. A CrN film with a thickness of 15 mn (N: 40 atomic percent), followed by argon gas, formazan, and nitrogen as a bond-killing gas to form a CrN film having a thickness of 65 n ^ ( (N: 1 〇 atomic percentage, c: i 〇 atomic percentage) ^ Thereafter, argon gas and nitrogen oxide gas were used as the (iv) gas to form a (10) film (N: 3 atomic percent, 〇: 3 atomic percent) having a thickness of 25 (four), and the film was continuously formed into a light-shielding film. The composition is a tilt film. The above process is used to fabricate a large mask base for FPD.

2130-9519-PF 22 200848918 ：疋在基板上形成半透光性膜的階段中横跨i線至 :線的波長頻寬的分光透過率。分光透過率藉由分光；:二 (曰立製相社侧）來敎。切由刀^度計 (光罩之製作） 接著，根據上述第2圖所示之 光罩製程製造亦W L , 边光丨生艇下置型之灰階 成 、 。此岭，關於由含有鉻和氮之材料所構 成的璲光性膜的蝕刻液，在 氯酸的蝕列@ ± ，旦吏用3有硝酸銨鈽和過 (評=㈣液’接觸時間（㈣時間）合計在2分鐘以内。 立光二之後的灰階部15中的分光透過率藉由… ^ (曰立製作所社製W⑽)來測定。最後，光罩製作前 後（光罩基底製作後和光罩 " 尤卓I作後）的灰階部1 5中橫跨i線 至g線的波長頻寬的透過率變化量減少為⑽以下。 、 又，在使用電子顯微鏡觀察灰階部15的表面（上面）的 表面狀態之後，看不出鉻系薄膜 挪別，夜之知蝕所導致的 顏吾。 再者，在使用電子顯微鏡觀察灰階部15的剖面（側面） 的表面狀態之後，看不出鉻系薄臈之餘刻液之侵餘所導致 的粗糙表面。 (弟4實施例） (光罩基底之製作） 基板使用了大型玻璃基板（合成石英（QZ)，厚度1〇_， 大小 850mmxl 200mm)。 在上述基板上’使用大型賤錢裝置，進行半透光性膜 2130-9519-PF 23 200848918 的薄膜形成。具體來說，使用石夕化组革巴材，將氯氣作為藏 鑛氣體，藉由κ磁控反應性㈣技術，形成 化 组脑）薄膜，作為半透光性膜。此薄膜組Γ為匕 Ta.Si-1:4(原子百分比）。 接著，在上述半透光性膜之上，形成由含有絡和氮之 材料所構成的遮光性膜。具體來說，使用絡革巴材，先將氯 氣和氮氣作為濺鍍氣體’形成厚度15η_Μ薄膜(以二 子百分比），接著將氬氣、甲烧、氮氣作為賤鍍氣體，形成 厚度65nm的CrCN薄膜（N:10原子百分比，子百分 比），然後’將氬氣和-氧化氮氣體作為濺鑛氣體，形成: 度25n„^Cr0N薄膜（N:3〇原子百分比，〇:3〇原子百分比）， 如此連續形成薄膜而成為遮光性膜。又，各層薄膜分別為 組成傾斜膜。 藉由以上的製程，製作FPD用大型光罩基底。 又測疋在基板上形成半透光性膜的階段中樺跨丨線至 g線的波長頻寬的分光透過率。分光透過率藉由分光光度 (日立製作所社製ϋ-4100)來測定。 。 (光罩之製作） "接著’根據上述第2圖所示之半透光性膜下置型之灰階 先罩製程製造光罩。此時，關於由含有鉻和氮之材料所構 成的遮光性膜的姓刻液，在常溫下使用含有石肖酸録鋪和過 m觸時間（_時間）合計在2分 (評估） 製作光罩之後的灰階部15中的分光透過率藉由分光光2130-9519-PF 22 200848918 : The spectral transmittance of the wavelength band across the i-line to the line in the stage of forming the semi-translucent film on the substrate. The spectral transmittance is obtained by spectroscopic; two (the side of the system). Cut by the knife (manufacture of the mask) Next, according to the mask process shown in Fig. 2 above, the manufacturing process is also W L , and the gray scale of the underside of the light boat is set. This ridge, about the etching solution of the luminescent film composed of the material containing chromium and nitrogen, in the etch of chloric acid @±, the use of 3 with ammonium nitrate and the (contact = (four) liquid' contact time ( (4) The total time is less than 2 minutes. The spectral transmittance in the gray scale portion 15 after the second light is measured by ... (W(10) manufactured by Seiko Seisakusho Co., Ltd.). Finally, before and after the mask is produced (after the mask base is produced and light) The amount of change in the transmittance of the wavelength band across the i-line to the g-line in the gray scale portion 15 of the cover "after the yushu I is reduced to (10) or less. Further, the gray scale portion 15 is observed using an electron microscope. After the surface state of the surface (top surface), the chrome-based film is not seen, and the eclipse caused by the night is not observed. After the surface state of the cross section (side surface) of the gray scale portion 15 is observed using an electron microscope, The rough surface caused by the remnant of the chrome-based thin enamel is not seen. (Example 4) (Mask substrate fabrication) The substrate is made of a large glass substrate (synthetic quartz (QZ), thickness 1 〇 _ , size 850mmxl 200mm). Use large money on the above substrate The film formation of the semi-transmissive film 2130-9519-PF 23 200848918 is carried out. Specifically, the chlorine gas is used as a mineral gas by using the shi magnetic resonance reactivity (four) technology. The membrane of the brain group is used as a semi-transmissive film. This film group is 匕 Ta.Si-1:4 (atomic percent). Next, a light-shielding film made of a material containing a complex and nitrogen is formed on the semi-translucent film. Specifically, using a tannery material, a chlorine gas and a nitrogen gas are first used as a sputtering gas to form a film having a thickness of 15 η Μ (in a percentage of two), and then argon gas, a methane gas, and nitrogen gas are used as a ruthenium plating gas to form a CrCN film having a thickness of 65 nm. (N: 10 atomic percent, sub-percentage), and then 'argon gas and nitrogen oxide gas as a splashing gas, forming: 25n ^ ^ Cr0N film (N: 3 atomic percent, 〇: 3 atomic percent), The thin film is continuously formed in this manner to form a light-shielding film. Further, each of the thin films is a composition of a tilted film. The above process is used to fabricate a large-sized photomask substrate for FPD, and the birch in the stage of forming a semi-transparent film on the substrate. The spectral transmittance of the wavelength band across the 丨 line to the g line. The spectral transmittance is measured by spectrophotometry (ϋ-4100 manufactured by Hitachi, Ltd.). (Mask production) "Next' according to Figure 2 above The glare-first mask process of the semi-transmissive film under-type is shown to produce a reticle. At this time, the etchant of the light-shielding film composed of the material containing chromium and nitrogen is used at room temperature. Recording and over m Time (_ Time) in 2 minutes in total (Evaluation) After the production of gray scale portion of the mask 15 in spectral transmittance by a spectrophotometer

2130-9519-PF 24 200848918 度計（曰立製作所社製U-41 00)來測定。最後，光罩製作前 後（光罩基底製作後和光罩製作後）的灰階部丨5中橫跨i線 至g線的波長頻寬的透過率變化量減少為3%以下。 又，在使用電子顯微鏡觀察灰階部丨5的表面（上面）的 表面狀態之後，看不出鉻系薄膜之蝕刻液之侵蝕所導致的 損害。 、 再者，在使用電子顯微鏡觀察灰階部丨5的剖面（側面） 的表面狀態之後，看不出鉻系薄膜之蝕刻液之侵蝕所導致 的粗趁表面。 (第1比較例） (光罩基底之製作） 基板使用了大型玻璃基板（合成石英（QZ)，厚度 大小 850mmxl 200mm)。 在上述基板上，使用大型濺鍍裝置，進行半透光性膜 的薄膜形成。具體來說，使用絲材，將氬氣作為減鑛氣 體’為使此半透光性膜在UM365nm)的波長中有權的透過 率’形成膜厚4nm的鈕（Ta)薄膜。 接著，在上述半透光性膜之上，形成由絡所構成的遮 先性膜。具體來說，使用鉻_，將氬氣作為㈣氣體， 开乂成厚度60nm的鉻薄膜而成為遮光性膜。 藉由以上的製程，製作FPD用大型光罩基底。 又，敎在基板上形成半透光性膜的階段中橫跨i線至 =的：長頻寬的分光透過率。分光透過率藉由分光光度計 (曰立製作所社製ϋ-41 0 0)來測定。2130-9519-PF 24 200848918 The meter (U-41 00, manufactured by Hitachi, Ltd.) was measured. Finally, the amount of change in transmittance of the wavelength band across the i-line to the g-line in the gray-scale portion 丨5 before and after the reticle fabrication (after the reticle substrate is formed and after the reticle is produced) is reduced to 3% or less. Further, after observing the surface state of the surface (upper surface) of the gray-scale portion 5 by an electron microscope, damage due to erosion of the etching liquid of the chromium-based film was not observed. Further, after observing the surface state of the cross section (side surface) of the gray-scale portion 丨5 using an electron microscope, the rough surface caused by the etching of the etching liquid of the chromium-based film was not observed. (First Comparative Example) (Production of Photomask Base) A large-sized glass substrate (synthetic quartz (QZ) having a thickness of 850 mm x 200 mm) was used for the substrate. On the above substrate, a thin film of a semi-translucent film was formed using a large sputtering apparatus. Specifically, a wire (Ta) film having a film thickness of 4 nm was formed by using a wire material and using argon gas as the decarburization gas 'having a transmittance of the semi-transmissive film at a wavelength of UM 365 nm. Next, a prepreg film composed of a network is formed on the semi-transmissive film. Specifically, chrome_ is used, and argon gas is used as a (four) gas, and a chromium thin film having a thickness of 60 nm is opened to form a light-shielding film. Through the above process, a large mask base for FPD is produced. Further, in the stage in which the semi-translucent film is formed on the substrate, the spectral transmittance of the long bandwidth spans from the i-line to the =. The spectral transmittance was measured by a spectrophotometer (ϋ-41 0 0 manufactured by Seiko Seisakusho Co., Ltd.).

2130-9519-PF 25 200848918 (光罩之製作） 接著’根據上述第2圖所示之半透光性膜下置型之灰产 光罩製程製造光罩。此時，關於絡膜的钱刻液，在常溫； 使用含有石肖酸錄鈽和過氯酸㈣刻液，接觸時間< 2 合计在2分鐘以内。 、 (評估） 製作光罩之後的灰階部丨5中的分光透過率藉由分光光 度計(日立製作所社製㈣。)來測定。最後，：罩二乍前 後（光罩基底製作後和光罩製作後）的灰階部15中橫跨i線 至g線的波長頻寬的透過率變化量增加至7%以上。 又，在使用電子顯微鏡觀察灰階部15的表面（上面）的 表面狀態之後’看得出鉻系薄膜之蝕刻液之侵蝕所導致的 損害。 再者，在使用電子顯微鏡觀察灰階部15的剖面（側面） 勺表面狀心之後’看知出鉻系薄膜之蝕刻液之侵蝕所導致 的粗糙表面。 (第2比較例） (光罩基底之製作） 基板使用了大型玻璃基板（合成石英⑽，厚度1〇麵， 大小 850mmxl 200_)。 *在上述基板上m型錢鍍裝£，進行半透光性膜 的薄艇形成。具體來說，择用知岔』 木兄便用鈕靶材，將氬氣作為濺鍍氣 體，形成膜厚4nm的鈕（Ta)薄膜作為半透光性膜。2130-9519-PF 25 200848918 (Production of Photomask) Next, a reticle is manufactured according to the ash mask process of the semi-transmissive film under-type shown in Fig. 2 described above. At this time, the money engraving solution about the collateral is at room temperature; the engraving containing tartaric acid and perchloric acid (iv) is used, and the contact time < 2 total is within 2 minutes. (Evaluation) The spectral transmittance in the gray scale portion 5 after the mask was produced was measured by a spectrophotometer (manufactured by Hitachi, Ltd. (4)). Finally, the amount of change in transmittance of the wavelength band across the i-line to the g-line in the gray scale portion 15 of the front and back of the cover (after the production of the mask base and after the mask is produced) is increased to 7% or more. Further, after observing the surface state of the surface (upper surface) of the gray scale portion 15 using an electron microscope, the damage caused by the etching of the etching liquid of the chromium-based film can be seen. Further, after observing the surface of the cross section (side surface) of the gray scale portion 15 using an electron microscope, the rough surface caused by the etching of the etching liquid of the chromium-based film was observed. (Second Comparative Example) (Production of Photomask Base) A large-sized glass substrate (synthetic quartz (10), thickness 1 , surface, size 850 mm×l 200 _) was used for the substrate. * On the above substrate, m-type money is plated, and a thin boat of semi-translucent film is formed. Specifically, it is a semi-transmissive film that uses a button target and uses argon gas as a sputtering gas to form a button (Ta) film having a thickness of 4 nm.

接著，在上述半透光性膜之上，形成由含有絡和氧之 2130-9519-PF 26 200848918 使用鉻革巴材，將氬氣Next, on the semi-transmissive film, 2130-9519-PF 26 containing 2008-0818 is used to form argon gas.

材料所構成的遮光性膜。具體來說 和氧氣的混合氣體作為濺鍍氣體， 膜，接著，將氬氣作為濺鍍氣體，开 然後，將氬氣和氧氣的混合氣體作 薄膜，如此連續形成薄膜而成為遮光性膜。此薄 膜組成為Cr :〇 = 2: 3 (原子百分比）。 藉由以上的製程，製作FPD用大型光罩基底。 又測疋在基板上形成半透光性膜的階段中橫跨丨線至 g線的波長頻寬的分光透過率。 (光罩之製作） 接著，根據上述第2圖所示之半透光性膜下置型之灰階 光罩製転製造光罩。此時，關於由氧化鉻膜的餘刻液，在 系ZfflL下使用§有硝酸錄鈽和過氯酸的蝕刻液，接觸時間（钱 刻時間）合計在2分鐘以内。 (評估） 製作光罩之後的灰階部丨5中的分光透過率藉由分光光 度計（曰立製作所社製U-4100)來測定。最後，光罩製作前 後（光罩基底製作後和光罩製作後）的灰階部1 5中橫跨i線 至g線的波長頻寬的透過率變化量增加至1 〇%以上。 又，在使用電子顯微鏡觀察灰階部1 5的表面（上面）的 表面狀態之後，看得出鉻系薄膜之蝕刻液之侵蝕所導致的 損害比第1比較例嚴重。 再者，在使用電子顯微鏡觀察灰階部丨5的剖面（侧面） 的表面狀態之後，看得出鉻系薄膜之蝕刻液之侵蝕所導致A light-shielding film composed of materials. Specifically, a mixed gas of oxygen is used as a sputtering gas, a film, and then argon gas is used as a sputtering gas. Then, a mixed gas of argon gas and oxygen gas is used as a film, and a thin film is continuously formed to form a light-shielding film. The composition of this film is Cr : 〇 = 2: 3 (atomic percent). Through the above process, a large mask base for FPD is produced. Further, the spectral transmittance of the wavelength band across the ridge line to the g line in the stage of forming the semi-transmissive film on the substrate was measured. (Production of Photomask) Next, a photomask was produced by a gray scale mask made of a semi-transmissive film underlying type shown in Fig. 2 described above. At this time, regarding the residual liquid of the chromium oxide film, an etching liquid having a nitric acid recording and perchloric acid was used under the system ZfflL, and the contact time (money time) was within 2 minutes. (Evaluation) The spectral transmittance in the gray scale portion 5 after the production of the mask was measured by a spectrophotometer (U-4100, manufactured by Seiko Seisakusho Co., Ltd.). Finally, the amount of change in transmittance of the wavelength band across the i-line to the g-line in the gray scale portion 15 after the reticle is formed (after the reticle substrate is formed and after the reticle is produced) is increased to 1% or more. Further, after observing the surface state of the surface (upper surface) of the gray scale portion 15 using an electron microscope, it was observed that the damage caused by the etching of the etching liquid of the chromium-based film was more serious than that of the first comparative example. Further, after observing the surface state of the cross section (side surface) of the gray-scale portion 丨5 using an electron microscope, it was observed that the etching liquid of the chromium-based film was eroded.

2130-9519-PF 27 200848918 的粗糙表面比第1比較例嚴重。 以上揭示了最佳實施例子來說明本發明，然而本發明 不受上述實施例所限定。 【圖式簡單說明】 第1圖為用來說明具有半透光性膜之灰階光罩的圖，第 1(A)圖為部分平面圖，第1(B)圖為部分剖面圖。 第2(A)〜（H)圖為用來說明半透朵 卞迄先性膜下置型之灰階光 罩及其製程的圖。 南壓水銀燈之分光分 第3圖為表示作為曝光光源之超 佈的圖。 【主要元件符號說明】 1 遮光部 1 ’ 和遮光部1對應的部分 2 透光部 2’ 和透光部2對應的部分 3 灰階部 3’ 和灰階部3對應的部分 3a 半透光性膜 13 遮光部 14 透光部 15 灰階部 16 透光性基板The rough surface of 2130-9519-PF 27 200848918 is more severe than the first comparative example. The preferred embodiments have been described above to illustrate the present invention, but the present invention is not limited by the above embodiments. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view for explaining a gray scale mask having a semi-translucent film, wherein Fig. 1(A) is a partial plan view, and Fig. 1(B) is a partial cross-sectional view. Fig. 2(A) to (H) are diagrams for explaining the gray scale mask of the semi-transparent film and the under-film type and the process thereof. Partial light split of the south pressure mercury lamp Fig. 3 is a view showing the super cloth as the exposure light source. [Description of main component symbols] 1 The light-shielding portion 1' corresponds to the portion 2 of the light-shielding portion 1 The light-transmitting portion 2' and the portion 3 corresponding to the light-transmitting portion 2 The gray-scale portion 3' and the portion 3a corresponding to the gray-scale portion 3 are semi-transparent Film 13 light-shielding portion 14 light-transmitting portion 15 gray-scale portion 16 light-transmitting substrate

2130-9519-PF 28 200848918 17 半透光性膜 18 透光性膜 20 光罩基底 21 第一光阻圖樣 22 遮光性膜圖樣 23 半透光性膜圖樣 24 第二光阻圖樣 30 灰階光罩 292130-9519-PF 28 200848918 17 Semi-transmissive film 18 Translucent film 20 Photomask substrate 21 First photoresist pattern 22 Light-shielding film pattern 23 Semi-transmissive film pattern 24 Second photoresist pattern 30 Gray-scale light Cover 29

2130-9519-PF2130-9519-PF

Claims (1)

200848918 十、申請專利範圍： 1 ·種光罩基底，用來製造平板顯示器裝置， 其特徵在於包括： 半透光性膜，由含有在上述基板上所形成之！旦的 所構成；及 基板； 遮光性膜，由含有在上述半透光性膜 氮的材料所構成。 之鉻和 、2·如申請專利範圍们項之光罩基底，其_， 述鉻和氮之材料的 有上 造，各層中含有鉻和氮。 数’構 3·如申請專利範圍第i項之光罩基底 餘刻液對由含有上汁 ’、 田使用鉻 膜進行絲Μ，㈣構成的遮光性 的半透光性膜的損傷 之材料所構成 構成的遮光性膜為鉻中含有氮的薄膜。气之材料的材料所 4·如申請專利範圍们項之光罩基 述纽之材料所構成的半透光性膜由如所成、中，由含有上 之材料、含㈣氮之材料、含氣和氧之㈣、含纽 材料中任一種材料所構成。 、“£和矽之 5· —種光罩，用來製造平板顯示器 其特徵在於： 〜 使用如申請專利範圍第1至4項中任一 製造。 項之光罩基底來 2130-9519-PF 30200848918 X. Patent application scope: 1 · A reticle substrate for manufacturing a flat panel display device, comprising: a semi-transparent film formed by being contained on the substrate! And the substrate; the light-shielding film is composed of a material containing the semi-transmissive film nitrogen. Chromium and 2, as in the reticle substrate of the patent application, the chrome and nitrogen materials are made up, and each layer contains chromium and nitrogen. The number of the structure is as follows: for example, the reticle base of the patent application scope i is a material for the damage of the light-shielding semi-transmissive film composed of the smear containing the smear, the chrome film used in the field, and (4) The light-shielding film which comprises a structure is a film which contains nitrogen in chromium. The material of the material of the gas is as follows: the semi-translucent film composed of the material of the reticle base of the patent application is made of the material containing the material, the material containing the nitrogen, and the It consists of any of the materials of gas and oxygen (4) and materials containing materials. , "£ and 矽 · · 种 种 种 种 种 种 种 种 种 种 种 种 种 种 种 种 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜
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