TW202138909A - Photomask blank, method of manufacturing photomask, and method of manufacturing display device - Google Patents

Photomask blank, method of manufacturing photomask, and method of manufacturing display device Download PDF

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TW202138909A
TW202138909A TW110122482A TW110122482A TW202138909A TW 202138909 A TW202138909 A TW 202138909A TW 110122482 A TW110122482 A TW 110122482A TW 110122482 A TW110122482 A TW 110122482A TW 202138909 A TW202138909 A TW 202138909A
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light
film
layer
photomask
shielding film
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TWI755337B (en
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坪井誠治
中村真実
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日商Ｈｏｙａ股份有限公司
馬來西亞商Hoya電子馬來西亞私人股份有限公司
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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
    • 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
    • G03F1/50—Mask blanks not covered by G03F1/20 - G03F1/34; 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
    • 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
    • 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
    • G03F7/70—Microphotolithographic exposure; Apparatus therefor
    • G03F7/708—Construction of apparatus, e.g. environment aspects, hygiene aspects or materials
    • G03F7/7095—Materials, e.g. materials for housing, stage or other support having particular properties, e.g. weight, strength, conductivity, thermal expansion coefficient
    • G03F7/70958—Optical materials or coatings, e.g. with particular transmittance, reflectance or anti-reflection properties

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  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Epidemiology (AREA)
  • Public Health (AREA)
  • Preparing Plates And Mask In Photomechanical Process (AREA)

Abstract

The present invention provides a photomask blank which is capable of obtaining a high-precision mask pattern when the photomask is formed by etching, and has optical characteristics capable of suppressing display unevenness when a display device is fabricated by using the photomask. The photomask blank of the present invention is characterized in that it is a photomask blank used for manufacturing a photomask used for manufacturing a display device, and provided with a transparent substrate composed of a material substantially transparent with respect to an exposure light; a light-shielding film arranged on the transparent substrate and composed of a material that is substantially opaque with respect to the exposure light; the light-shielding film is provided with, from the side of the transparent substrate, a first reflection suppressing layer, a light-shielding layer, and a second reflection suppressing layer, wherein the first reflection suppressing layer is a chromium-based material containing chromium, oxygen, and nitrogen, and has a composition of a content ratio of chromium from 25 to 75 atom%, a content ratio of oxygen form 15 to 45 atom%, and a content ratio of nitrogen from 10 to 30 atom%, the light-shielding layer is a chromium-based material containing chromium and nitrogen, and has a composition of a content ratio of chromium from 70 to 95 atom% and a content ratio of nitrogen from 5 to 30 atom%, the second reflection suppressing layer is a chromium-base material containing chromium, oxygen, and nitrogen and has a composition of a content ratio of chromium from 30 to 75 atom%, a content ratio of oxygen from 20 to 50 atom%, and a content ratio of nitrogen from 5 to 20 atom%, so that the reflective indexes of the front and back surfaces of the light-shielding film with respect to the light exposure wavelength of the exposure light are respectively 10% or less, and the thickness of the first reflection suppressing layer, the light-shielding layer, and the second reflection suppressing layer are set in such a way that the optical density is 3.0 or more.

Description

光罩基底、光罩之製造方法、以及顯示裝置製造方法Mask substrate, mask manufacturing method, and display device manufacturing method

本發明係關於一種光罩基底及其製造方法、光罩之製造方法、以及顯示裝置製造方法。The present invention relates to a photomask substrate and a manufacturing method thereof, a manufacturing method of a photomask, and a manufacturing method of a display device.

於以LCD(Liquid Crystal Display，液晶顯示器)為代表之FPD(Flat Panel Display，平板顯示器)等顯示裝置中，隨著大畫面化、廣視角化，高精細化、高速顯示化正急速發展。為了該高精細化、高速顯示化而需要之要素之一為製作微細且尺寸精度較高之元件或配線等電子電路圖案。該顯示裝置用電子電路之圖案化多使用光微影。因此，需要形成有微細且高精度之圖案的顯示裝置製造用之光罩。In display devices such as FPD (Flat Panel Display) represented by LCD (Liquid Crystal Display), as large screens and wide viewing angles, high-definition and high-speed displays are rapidly developing. One of the elements required for this high-definition and high-speed display is the production of electronic circuit patterns such as components or wirings with fine and high dimensional accuracy. The patterning of the electronic circuit for the display device mostly uses photolithography. Therefore, there is a need for a mask for manufacturing a display device formed with a fine and high-precision pattern.

顯示裝置製造用之光罩係由光罩基底製作。光罩基底係於由合成石英玻璃等構成之透明基板上設置由相對於曝光光不透明之材料構成之遮光膜而構成。於光罩基底或光罩中，為了抑制曝光時之光之反射，而於遮光膜之正背兩面側設置有反射抑制層，光罩基底例如成為自透明基板側依次使第1反射抑制層、遮光層及第2反射抑制層積層而成之膜構成。光罩係藉由將光罩基底之遮光膜利用濕式蝕刻等進行圖案化並形成特定之遮罩圖案而製作。The photomask used in the manufacture of the display device is made of the photomask substrate. The mask base is formed by setting a light-shielding film made of a material that is opaque to exposure light on a transparent substrate made of synthetic quartz glass or the like. In the mask base or mask, in order to suppress the reflection of light during exposure, reflection suppression layers are provided on the front and back sides of the light-shielding film. The light-shielding layer and the second reflection suppression layer are laminated. The photomask is made by patterning the light-shielding film of the photomask base by wet etching or the like and forming a specific mask pattern.

與此種顯示裝置製造用之光罩、成為其原版之光罩基底、以及兩者之製造方法相關聯之技術揭示於專利文獻1。 [先前技術文獻] [專利文獻]The technology associated with the photomask used for manufacturing such a display device, the photomask substrate that becomes the original version, and the manufacturing methods of both are disclosed in Patent Document 1. [Prior Technical Literature] [Patent Literature]

[專利文獻1]韓國註冊專利第10-1473163號公報[Patent Document 1] Korean Registered Patent No. 10-1473163

[發明所欲解決之問題][The problem to be solved by the invention]

於顯示裝置(例如TV(TeleVision，電視)用之顯示面板)之製造中，例如，使用光罩，對顯示裝置用基板轉印特定圖案之後，使顯示裝置用基板滑動，轉印特定圖案，藉此，重複進行圖案轉印。於該轉印中，因自曝光裝置之光源而曝光光入射至光罩時之光罩之背面側之反射光、或曝光光通過光罩後來自被轉印體之反射光返回至光罩正面側之反射光之影響，有時於顯示裝置之重疊附近，照射假定以上之曝光光。其結果，有時以相鄰之圖案彼此一部分重疊之方式曝光，而於所製造之顯示裝置中產生顯示不均。In the manufacture of display devices (such as display panels for TV (TeleVision, television)), for example, a photomask is used to transfer a specific pattern to the substrate for the display device, and then the substrate for the display device is slid to transfer the specific pattern. Thus, pattern transfer is repeated. In this transfer, the reflected light from the back side of the photomask when the exposure light from the light source of the exposure device is incident on the photomask, or the reflected light from the transferred body after the exposure light passes through the photomask, returns to the front side of the photomask The influence of the reflected light on the side is sometimes in the vicinity of the overlap of the display device, and the exposure light above the assumption is irradiated. As a result, it is sometimes exposed in such a way that adjacent patterns partially overlap each other, which may cause display unevenness in the manufactured display device.

因此，於光罩基底中，為了抑制顯示不均而要求使遮光膜之正背面之反射率為10%以下(例如，波長365 nm～436 nm)，進而較佳為5%以下(例如，400 nm～436 nm)。進而，自提高光罩之CD均勻性之觀點而言，若考慮雷射描畫光中之遮光膜之正面反射，則要求使遮光膜正面之反射率為5%以下(例如，波長413 nm)，進而較佳為3%以下(例如，波長413 nm)。Therefore, in the mask substrate, in order to suppress display unevenness, it is required that the reflectance of the front and back surfaces of the light-shielding film is 10% or less (for example, the wavelength of 365 nm to 436 nm), and more preferably 5% or less (for example, 400 nm～436 nm). Furthermore, from the viewpoint of improving the CD uniformity of the mask, if the front reflection of the light-shielding film in the laser drawing light is considered, it is required that the reflectivity of the front side of the light-shielding film is 5% or less (for example, a wavelength of 413 nm). More preferably, it is 3% or less (for example, a wavelength of 413 nm).

又，顯示裝置製造用之光罩係除了顯示裝置之高精細化、高速顯示化之要求以外，基板尺寸趨於大型化，近年來，將使用短邊之長度為850 mm以上之矩形狀基板之超大型之光罩使用於顯示裝置之製造。再者，作為上述短邊之長度為850 mm以上之大型光罩，有G7用之850 mm×1200 mm尺寸、G8用之1220 mm×1400 mm尺寸、G10用之1620 mm×1780 mm尺寸，尤其作為此種大型之光罩中之遮罩圖案之CD均勻性(CD Uniformity)要求100 nm以下之高精度之遮罩圖案。In addition, in addition to the requirements for high-definition and high-speed display of display devices, photomasks used in the manufacture of display devices have become larger in size. In recent years, rectangular substrates with shorter sides of 850 mm or more will be used. The super-large mask is used in the manufacture of display devices. In addition, as the above-mentioned large-scale photomask with a short side length of 850 mm or more, there are 850 mm×1200 mm size for G7, 1220 mm×1400 mm size for G8, and 1620 mm×1780 mm size for G10, especially The CD Uniformity, which is the mask pattern in this large mask, requires a high-precision mask pattern below 100 nm.

於先前提出之專利文獻1之光罩基底中，於使基板之短邊之長度為850 mm以上之情形時，無法滿足使遮光膜之正背面之反射率相對於曝光波長為10%以下、且使用光罩基底製作出之光罩中之遮罩圖案之CD均勻性為100 nm以下的要求。In the previously proposed photomask base of Patent Document 1, when the length of the short side of the substrate is 850 mm or more, the reflectivity of the front and back of the light-shielding film cannot be set to 10% or less with respect to the exposure wavelength, and The CD uniformity of the mask pattern in the mask made by using the mask substrate is below 100 nm.

本發明之目的在於提供一種於藉由蝕刻而製作光罩時獲得高精度之遮罩圖案、且滿足如於使用光罩製作顯示裝置時可抑制顯示不均之光學特性的光罩基底。 [解決問題之技術手段]The object of the present invention is to provide a mask substrate that obtains a high-precision mask pattern when the mask is manufactured by etching, and satisfies the optical characteristics of suppressing uneven display when the mask is used to manufacture a display device. [Technical means to solve the problem]

(構成1) 一種光罩基底，其特徵在於：其係於製作顯示裝置製造用之光罩時使用之光罩基底，且具有： 透明基板，其由相對於曝光光實質上透明之材料而構成； 遮光膜，其設置於上述透明基板上，且由相對於上述曝光光實質上不透明之材料而構成； 上述遮光膜係自上述透明基板側起具備第1反射抑制層、遮光層及第2反射抑制層， 上述第1反射抑制層係含有鉻、氧及氮之鉻系材料，且具有鉻之含有率為25～75原子%、氧之含有率為15～45原子%、氮之含有率為10～30原子%之組成， 上述遮光層係含有鉻與氮之鉻系材料，且具有鉻之含有率為70～95原子%、氮之含有率為5～30原子%之組成， 上述第2反射抑制層係含有鉻、氧及氮之鉻系材料，且具有鉻之含有率為30～75原子%、氧之含有率為20～50原子%、氮之含有率為5～20原子%之組成， 以使上述遮光膜之正面及背面之相對於上述曝光光之曝光波長之反射率分別為10%以下，且光學濃度成為3.0以上之方式，設定上述第1反射抑制層、上述遮光層、及上述第2反射抑制層之膜厚。(Composition 1) A photomask substrate, which is characterized in that it is a photomask substrate used when manufacturing a photomask for manufacturing a display device, and has: A transparent substrate, which is composed of a material that is substantially transparent to the exposure light; A light-shielding film, which is provided on the above-mentioned transparent substrate and is made of a material that is substantially opaque with respect to the above-mentioned exposure light; The light-shielding film includes a first reflection-inhibiting layer, a light-shielding layer, and a second reflection-inhibiting layer from the transparent substrate side, and The first reflection suppression layer is a chromium-based material containing chromium, oxygen and nitrogen, and has a chromium content of 25 to 75 atomic %, an oxygen content of 15 to 45 atomic %, and a nitrogen content of 10 to 30 The composition of atomic %, The light-shielding layer is a chromium-based material containing chromium and nitrogen, and has a composition with a chromium content of 70 to 95 atomic% and a nitrogen content of 5 to 30 atomic %. The second reflection suppression layer is a chromium-based material containing chromium, oxygen, and nitrogen, and has a chromium content of 30 to 75 atomic %, an oxygen content of 20 to 50 atomic %, and a nitrogen content of 5 to 20 The composition of atomic %, The first reflection suppressing layer, the light-shielding layer, and the above-mentioned first reflection suppressing layer, the above-mentioned light-shielding layer, and the above-mentioned The film thickness of the second reflection suppression layer.

(構成2) 如構成1之光罩基底，其特徵在於：上述第1反射抑制層係鉻之含有率為50～75原子%，氧之含有率為15～35原子%，氮之含有率為10～25原子%， 上述第2反射抑制層係鉻之含有率為50～75原子%，氧之含有率為20～40原子%，氮之含有率為5～20原子%。(Composition 2) Such as the mask substrate of composition 1, characterized in that the content of the first reflection suppression layer is 50 to 75 atomic %, the content of oxygen is 15 to 35 atomic %, and the content of nitrogen is 10 to 25 atomic% %, The chromium content of the second reflection suppression layer is 50 to 75 atomic %, the oxygen content is 20 to 40 atomic %, and the nitrogen content is 5 to 20 atomic %.

(構成3) 如構成1或2之光罩基底，其特徵在於：上述第1反射抑制層及上述第2反射抑制層分別具有氧及氮中至少任一個元素之含有率沿著膜厚方向而連續地或階段性地發生組成變化之區域。(Composition 3) For example, the mask substrate of composition 1 or 2, characterized in that: the first reflection suppression layer and the second reflection suppression layer respectively have at least one element of oxygen and nitrogen. The content of at least one element is continuously or stepwise along the film thickness direction. The area where compositional changes occur sexually.

(構成4) 如構成1至3中任一項之光罩基底，其特徵在於：上述第2反射抑制層具有朝向膜厚方向之上述遮光層側而氧之含有率增加之區域。(Composition 4) The mask substrate of any one of components 1 to 3 is characterized in that the second reflection suppression layer has a region where the oxygen content increases toward the light shielding layer side in the film thickness direction.

(構成5) 如構成1至4中任一項之光罩基底，其特徵在於：上述第2反射抑制層具有朝向膜厚方向之上述遮光層側而氮之含有率降低之區域。(Composition 5) The mask base of any one of components 1 to 4 is characterized in that the second reflection suppression layer has a region where the nitrogen content decreases toward the light-shielding layer side in the film thickness direction.

(構成6) 如構成1至5中任一項之光罩基底，其特徵在於：上述第1反射抑制層具有朝向膜厚方向之上述透明基板而氧之含有率增加並且氮之含有率降低之區域。(Composition 6) The mask base of any one of components 1 to 5 is characterized in that the first reflection suppression layer has a region where the transparent substrate faces the film thickness direction and the oxygen content is increased and the nitrogen content is decreased.

(構成7) 如構成1至6中任一項之光罩基底，其特徵在於：上述第2反射抑制層係以氧之含有率較上述第1反射抑制層變高之方式構成。(Composition 7) The photomask substrate of any one of components 1 to 6, characterized in that the second reflection suppression layer is configured such that the oxygen content is higher than that of the first reflection suppression layer.

(構成8) 如構成1至7中任一項之光罩基底，其特徵在於：上述第1反射抑制層係以氮之含有率較上述第2反射抑制層變高之方式構成。(Composition 8) The mask substrate of any one of components 1 to 7, characterized in that the first reflection suppression layer is configured such that the nitrogen content is higher than that of the second reflection suppression layer.

(構成9) 如構成1至8中任一項之光罩基底，其特徵在於：上述遮光層包含鉻(Cr)與氮化二鉻(Cr2 N)。(Configuration 9) The mask substrate of any one of the configurations 1 to 8, characterized in that the light shielding layer contains chromium (Cr) and chromium nitride (Cr 2 N).

(構成10) 如構成1至9中任一項之光罩基底，其中上述第1反射抑制層及上述第2反射抑制層包含氮化鉻(CrN)、氧化鉻(III)(Cr2 O3 )及氧化鉻(VI)(CrO3 )。(Configuration 10) As the mask base of any one of the configurations 1 to 9, wherein the first reflection suppression layer and the second reflection suppression layer include chromium nitride (CrN), chromium oxide (III) (Cr 2 O 3 ) And chromium oxide (VI) (CrO 3 ).

(構成11) 如構成1至10中任一項之光罩基底，其特徵在於：上述透明基板係矩形狀之基板，該基板之短邊之長度為850 mm以上且1620 mm以下。(Composition 11) For example, the mask base constituting any one of 1 to 10 is characterized in that the transparent substrate is a rectangular substrate, and the length of the short side of the substrate is 850 mm or more and 1620 mm or less.

(構成12) 如構成1至11中任一項之光罩基底，其特徵在於：於上述透明基板與上述遮光膜之間，進而具備具有較上述遮光膜之光學濃度低之光學濃度的半透光膜。(Composition 12) The mask base of any one of components 1 to 11 is characterized in that between the transparent substrate and the light-shielding film, a semi-transmissive film having an optical density lower than that of the light-shielding film is further provided.

(構成13) 如構成1至11中任一項之光罩基底，其特徵在於：於上述透明基板與上述遮光膜之間進而具備相位偏移膜。(Composition 13) The mask base of any one of compositions 1 to 11 is characterized in that a phase shift film is further provided between the transparent substrate and the light-shielding film.

(構成14) 一種光罩基底之製造方法，其特徵在於：其係於製作顯示裝置製造用之光罩時使用的光罩基底之製造方法，該光罩係於由相對於曝光光實質上透明之材料而構成之透明基板上藉由濺鍍法而形成由相對於曝光光實質上不透明之材料而構成之遮光膜者，且具有如下步驟： 於上述透明基板上，藉由使用包含鉻之濺鍍靶、與包含含有氧系氣體、氮系氣體之反應性氣體與稀有氣體之濺鍍氣體之反應性濺鍍，而形成第1反射抑制層，該第1反射抑制層係含有鉻、氧及氮之鉻系材料且具有鉻之含有率為25～75原子%、氧之含有率為15～45原子%、氮之含有率為10～30原子%之組成； 於上述第1反射抑制層上，藉由使用包含鉻之濺鍍靶、與包含含有氮系氣體之反應性氣體與稀有氣體之濺鍍氣體的反應濺鍍，而形成遮光層，該遮光層係含有鉻與氮之鉻系材料且具有鉻之含有率為70～95原子%、氮之含有率為5～30原子%之組成；及 於上述遮光層上，藉由使用包含鉻之濺鍍靶、與包含含有氧系氣體、氮系氣體之反應性氣體與稀有氣體之濺鍍氣體之反應性濺鍍，而形成第2反射抑制層，該第2反射抑制層係含有鉻、氧及氮之鉻系材料且具有鉻含有率為30～75原子%、氧之含有率為20～50原子%、氮之含有率為5～20原子%之組成； 上述反應性濺鍍中，濺鍍氣體中所包含之反應性氣體之流量係選擇成為金屬模式之流量，以上述遮光膜之正面及背面之相對於上述曝光光之曝光波長之反射率分別為10%以下，且光學濃度成為3.0以上之方式，形成上述第1反射抑制層、上述遮光層、及上述第2反射抑制層之膜厚。(Composition 14) A method of manufacturing a photomask substrate, characterized in that it is a manufacturing method of a photomask substrate used when manufacturing a photomask for manufacturing a display device, and the photomask is made of a material that is substantially transparent to exposure light. A light-shielding film made of a material that is substantially opaque to the exposure light is formed on the transparent substrate by a sputtering method, and has the following steps: On the above-mentioned transparent substrate, by using a sputtering target containing chromium, reactive sputtering with a sputtering gas containing a reactive gas containing oxygen-based gas, nitrogen-based gas, and a rare gas, the first reflection suppression layer is formed , The first reflection suppression layer is a chromium-based material containing chromium, oxygen and nitrogen and has a chromium content rate of 25 to 75 atomic %, an oxygen content rate of 15 to 45 atomic percent, and a nitrogen content rate of 10 to 30 The composition of atomic %; On the first reflection suppression layer, a light-shielding layer is formed by reactive sputtering using a sputtering target containing chromium and a sputtering gas containing a reactive gas containing a nitrogen-based gas and a rare gas A chromium-based material containing chromium and nitrogen, with a chromium content rate of 70 to 95 atomic%, and a nitrogen content rate of 5 to 30 atomic%; and On the above-mentioned light-shielding layer, a second reflection suppression layer is formed by reactive sputtering using a sputtering target containing chromium, and a sputtering gas containing a reactive gas containing oxygen-based gas, nitrogen-based gas, and a rare gas The second reflection suppression layer is a chromium-based material containing chromium, oxygen and nitrogen and has a chromium content of 30 to 75 atomic %, an oxygen content of 20 to 50 atomic %, and a nitrogen content of 5 to 20 atomic% % Of the composition; In the above reactive sputtering, the flow rate of the reactive gas contained in the sputtering gas is selected to be the flow rate of the metal mode, and the reflectivity of the front and back of the light shielding film with respect to the exposure wavelength of the exposure light is 10 respectively % Or less and the optical density becomes 3.0 or more to form the film thicknesses of the first reflection suppression layer, the light shielding layer, and the second reflection suppression layer.

(構成15) 如構成14之光罩基底之製造方法，其特徵在於：上述氧系氣體為氧(O2 )氣體。(Composition 15) The method for manufacturing the mask substrate of the composition 14 is characterized in that the oxygen-based gas is oxygen (O 2 ) gas.

(構成16) 如構成14或15之光罩基底之製造方法，其特徵在於：上述第1反射抑制層、上述遮光層及上述第2反射抑制層係使用一面使上述透明基板相對於上述濺鍍靶而相對性地移動一面成膜上述遮光膜之線內型濺鍍裝置而形成。(Composition 16) The manufacturing method of the mask base of the composition 14 or 15, characterized in that the first reflection suppression layer, the light shielding layer, and the second reflection suppression layer are made by using one side so that the transparent substrate is opposite to the sputtering target It is formed by moving one side of the in-line sputtering device for forming the above-mentioned light-shielding film.

(構成17) 如構成14至16中任一項之光罩基底之製造方法，其特徵在於：於上述透明基板與上述遮光膜之間，形成具有較上述遮光膜之光學濃度低之光學濃度的半透光膜。(Composition 17) The method for manufacturing a mask base of any one of 14 to 16, characterized in that: between the transparent substrate and the light-shielding film, a semi-transmissive film having an optical density lower than that of the light-shielding film is formed .

(構成18) 如構成14至16中任一項之光罩基底之製造方法，其特徵在於：於上述透明基板與上述遮光膜之間形成相位偏移膜。(Composition 18) The manufacturing method of the mask base of any one of 14 to 16 is characterized in that a phase shift film is formed between the transparent substrate and the light-shielding film.

(構成19) 一種光罩之製造方法，其特徵在於具有如下步驟： 準備如構成1至11中任一項之上述光罩基底；及 於上述遮光膜上形成抗蝕劑膜，將自上述抗蝕劑膜形成之抗蝕劑圖案作為遮罩對上述遮光膜進行蝕刻而於上述透明基板上形成遮光膜圖案。(Composition 19) A method for manufacturing a photomask, which is characterized by the following steps: Prepare the above-mentioned photomask substrate as constituting any one of 1 to 11; and A resist film is formed on the light-shielding film, and the light-shielding film is etched using the resist pattern formed from the resist film as a mask to form a light-shielding film pattern on the transparent substrate.

(構成20) 一種光罩之製造方法，其特徵在於具有如下步驟： 準備如構成12之上述光罩基底； 於上述遮光膜上形成抗蝕劑膜，將自上述抗蝕劑膜形成之抗蝕劑圖案作為遮罩對上述遮光膜進行蝕刻而於上述透明基板上形成遮光膜圖案；及 將上述遮光膜圖案作為遮罩對上述半透光膜進行蝕刻而於上述透明基板上形成半透光膜圖案。(Composition 20) A method for manufacturing a photomask, which is characterized by the following steps: Prepare the above-mentioned photomask substrate as composition 12; Forming a resist film on the light-shielding film, etching the light-shielding film using the resist pattern formed from the resist film as a mask to form a light-shielding film pattern on the transparent substrate; and The translucent film is etched using the light-shielding film pattern as a mask to form a translucent film pattern on the transparent substrate.

(構成21) 一種光罩之製造方法，其特徵在於具有如下步驟： 準備如構成13之上述光罩基底； 於上述遮光膜上形成抗蝕劑膜，將自上述抗蝕劑膜形成之抗蝕劑圖案作為遮罩對上述遮光膜進行蝕刻而於上述透明基板上形成遮光膜圖案；及 將上述遮光膜圖案作為遮罩對上述相位偏移膜進行蝕刻而於上述透明基板上形成相位偏移膜圖案。(Composition 21) A method for manufacturing a photomask, which is characterized by the following steps: Prepare the above-mentioned photomask substrate as structure 13; Forming a resist film on the light-shielding film, etching the light-shielding film using the resist pattern formed from the resist film as a mask to form a light-shielding film pattern on the transparent substrate; and The phase shift film is etched using the light-shielding film pattern as a mask to form a phase shift film pattern on the transparent substrate.

(構成22) 一種顯示裝置之製造方法，其特徵在於具有曝光步驟，該曝光步驟係將藉由如構成19至21中任一項之光罩之製造方法而獲得之光罩載置於曝光裝置之遮罩載台，將形成於上述光罩上之上述遮光膜圖案、上述半透光膜圖案、上述相位偏移膜圖案之至少一個遮罩圖案曝光轉印至形成於顯示裝置基板上之抗蝕劑。 [發明之效果](Composition 22) A method for manufacturing a display device, characterized by having an exposure step, the exposure step is to mount the mask obtained by the method for manufacturing a mask as in any one of 19 to 21 on the mask of the exposure device A stage for exposing and transferring at least one mask pattern of the light-shielding film pattern, the semi-transparent film pattern, and the phase shift film pattern formed on the photomask to a resist formed on a substrate of a display device. [Effects of Invention]

根據本發明，獲得一種可製造出圖案精度優異、且具有如於顯示裝置之製造時可抑制顯示不均之光學特性之光罩的光罩基底。According to the present invention, it is possible to obtain a photomask substrate capable of manufacturing a photomask having excellent pattern accuracy and optical characteristics that can suppress display unevenness during the manufacture of a display device.

以下，一面參照圖式一面對本發明之實施形態具體地進行說明。再者，以下之實施形態係使本發明具體化時之一形態，並不將本發明限定於其範圍內。再者，有時於圖中對相同或相當之部分標註相同之符號而將其說明簡化或省略。Hereinafter, the embodiments of the present invention will be specifically described with reference to the drawings. In addition, the following embodiment is an aspect when the present invention is embodied, and the present invention is not limited to the scope thereof. In addition, the same or equivalent parts may be denoted by the same reference numerals in the drawings, and the description thereof may be simplified or omitted.

＜光罩基底＞ 對本發明之一實施形態之光罩基底進行說明。本實施形態之光罩基底係於製作使自例如300 nm～550 nm之波長區域選擇之單波長之光曝光、或使包含複數個波長之光(例如，j射線(波長313 nm)、i射線(波長365 nm)、h射線(405 nm)、g射線(波長436 nm))之複合光曝光的顯示裝置製造用光罩時使用。再者，於本說明書中使用「～」表示之數值範圍係指包含「～」之前後所記載之數值作為下限值及上限值之範圍。＜Mask base＞ The photomask substrate of one embodiment of the present invention will be described. The mask substrate of this embodiment is made to expose light of a single wavelength selected from a wavelength region of, for example, 300 nm to 550 nm, or to expose light of multiple wavelengths (for example, j-ray (wavelength: 313 nm), i-ray (Wavelength 365 nm), h-ray (405 nm), g-ray (wavelength 436 nm)) combined light exposure used for display device manufacturing masks. In addition, the numerical range indicated by "～" in this manual refers to the range that includes the numerical value described before and after "～" as the lower limit and the upper limit.

圖1係表示本發明之一實施形態之光罩基底之概略構成之剖視圖。光罩基底1係具備透明基板11及遮光膜12而構成。以下，作為本發明之一實施形態之光罩基底，對光罩之遮罩圖案(轉印圖案)為遮光膜圖案之二元型之光罩基底進行說明。Fig. 1 is a cross-sectional view showing a schematic configuration of a photomask substrate according to an embodiment of the present invention. The mask base 1 is configured by including a transparent substrate 11 and a light shielding film 12. Hereinafter, as a mask base of one embodiment of the present invention, a binary type mask base in which the mask pattern (transfer pattern) of the mask is a light-shielding film pattern will be described.

(透明基板) 透明基板11係由相對於曝光光實質上透明之材料而形成，只要為具有透光性之基板則並不特別限定。使用相對於曝光波長之透過率為85%以上，較佳為90%以上之基板材料。作為形成透明基板11之材料，例如，可列舉合成石英玻璃、鈉鈣玻璃、無鹼玻璃、低熱膨脹玻璃。(Transparent substrate) The transparent substrate 11 is formed of a material that is substantially transparent to exposure light, and it is not particularly limited as long as it is a transparent substrate. Use a substrate material whose transmittance relative to the exposure wavelength is 85% or more, preferably 90% or more. Examples of the material forming the transparent substrate 11 include synthetic quartz glass, soda lime glass, alkali-free glass, and low thermal expansion glass.

透明基板11之大小可根據顯示裝置製造用之光罩所要求之大小而適當變更。例如，作為透明基板11，可使用矩形狀之基板，且其短邊之長度為330 mm以上且1620 mm以下之大小之透明基板11。作為透明基板11，例如，可使用大小為330 mm×450 mm、390 mm×610 mm、500 mm×750 mm、520 mm×610 mm、520 mm×800 mm、800×920 mm、850 mm×1200 mm、850 mm×1400 mm、1220 mm×1400 mm、1620 mm×1780 mm等基板。尤其，較佳為基板之短邊之長度為850 mm以上且1620 mm以下。藉由使用此種透明基板11，而獲得G7～G10之顯示裝置製造用之光罩。The size of the transparent substrate 11 can be appropriately changed according to the required size of the mask used for manufacturing the display device. For example, as the transparent substrate 11, a rectangular substrate can be used, and the length of the short side of the transparent substrate 11 is 330 mm or more and 1620 mm or less. As the transparent substrate 11, for example, sizes of 330 mm × 450 mm, 390 mm × 610 mm, 500 mm × 750 mm, 520 mm × 610 mm, 520 mm × 800 mm, 800 × 920 mm, 850 mm × 1200 can be used. mm, 850 mm×1400 mm, 1220 mm×1400 mm, 1620 mm×1780 mm and other substrates. In particular, it is preferable that the length of the short side of the substrate is 850 mm or more and 1620 mm or less. By using such a transparent substrate 11, a photomask for manufacturing display devices of G7 to G10 is obtained.

(遮光膜) 遮光膜12係自透明基板11側依次積層有第1反射抑制層13、遮光層14及第2反射抑制層15而構成。再者，以下，將光罩基底1之透明基板11側設為背面側，將遮光膜12側設為正面側而進行說明。(Shading film) The light-shielding film 12 is constituted by laminating a first reflection suppression layer 13, a light-shielding layer 14, and a second reflection suppression layer 15 in this order from the transparent substrate 11 side. In addition, in the following description, the transparent substrate 11 side of the mask base 1 is referred to as the back side, and the light shielding film 12 side is referred to as the front side.

第1反射抑制層13係於遮光膜12中，設置於遮光層14之接近透明基板11之側之面，於使用利用光罩基底1製作出之光罩進行圖案轉印之情形時，配置於接近曝光光源之側。於使用光罩進行曝光處理之情形時，自光罩之透明基板11側(背面側)照射曝光光，將圖案轉印像轉印至形成於作為被轉印體之顯示裝置用基板上之抗蝕劑膜。此時，若曝光光由遮光膜圖案之背面側反射，則有時成為作為遮光膜圖案之遮罩圖案之雜散光，而產生重影像之形成或眩光量之增加等轉印像之劣化，或於顯示裝置用基板之重疊附近，照射假定以上之曝光光，而產生顯示不均。第1反射抑制層13於使用光罩進行圖案轉印時，由於可抑制遮光膜12之背面側之曝光光之反射，故而可抑制轉印像之劣化而有助於轉印特性之提高，並且於顯示裝置用基板之重疊附近，可抑制由照射假定以上之曝光光所致之顯示不均之產生。The first reflection suppression layer 13 is in the light-shielding film 12, and is provided on the side of the light-shielding layer 14 close to the transparent substrate 11. When pattern transfer is performed using a photomask made by using the photomask base 1, it is placed on Close to the side of the exposure light source. When a photomask is used for exposure processing, exposure light is irradiated from the transparent substrate 11 side (rear side) of the photomask to transfer the pattern transfer image to the resist formed on the substrate for the display device as the transferred body. Etching agent film. At this time, if the exposure light is reflected from the back side of the light-shielding film pattern, it sometimes becomes stray light of the mask pattern as the light-shielding film pattern, which may cause the formation of double images or increase the amount of glare and other transfer image deterioration, or In the vicinity of the overlap of the substrate for the display device, the exposure light above the assumption is irradiated, resulting in display unevenness. The first reflection suppression layer 13 can suppress the reflection of exposure light on the back side of the light-shielding film 12 when pattern transfer is performed using a photomask, thereby suppressing the deterioration of the transferred image and contributing to the improvement of transfer characteristics, and In the vicinity of the overlap of the substrate for the display device, it is possible to suppress the occurrence of display unevenness caused by irradiating the above-presumed exposure light.

遮光層14係於遮光膜12中設置於第1反射抑制層13與第2反射抑制層15之間。遮光層14具有以遮光膜12具有用以相對於曝光光實質上不透明之光學濃度之方式調整的功能。此處，所謂相對於曝光光實質上不透明，係指以光學濃度計為3.0以上之遮光性，自轉印特性之觀點而言，較佳為光學濃度為4.0以上，進而較佳為4.5以上較佳。The light-shielding layer 14 is provided in the light-shielding film 12 between the first reflection suppression layer 13 and the second reflection suppression layer 15. The light-shielding layer 14 has a function of adjusting the optical density of the light-shielding film 12 to be substantially opaque with respect to exposure light. Here, the term "substantially opaque with respect to exposure light" means a light-shielding property of 3.0 or more in terms of optical density. From the viewpoint of transfer characteristics, the optical density is preferably 4.0 or more, more preferably 4.5 or more. .

第2反射抑制層15係於遮光膜12中，設置於遮光層14之遠離透明基板11之側之面。第2反射抑制層15係於在其上形成抗蝕劑膜並對該抗蝕劑膜藉由描畫裝置(例如雷射描畫裝置)之描畫光(雷射光)而描畫特定圖案時，可抑制遮光膜12之正面側之反射，故而可提高抗蝕劑圖案以及基於其形成之遮罩圖案之CD均勻性(CD Uniformity)。又，第2反射抑制層15於用作光罩之情形時，配置於作為被轉印體之顯示裝置用基板側，可抑制由被轉印體反射之光由光罩之遮光膜12之正面側再次反射後返回至被轉印體，抑制轉印像之劣化而有助於轉印特性之提高，並且可於顯示裝置用基板之重疊附近，抑制由照射假定以上之曝光光所致之顯示不均之產生。The second reflection suppression layer 15 is in the light-shielding film 12 and is provided on the side of the light-shielding layer 14 away from the transparent substrate 11. The second reflection suppression layer 15 can suppress light shielding when a resist film is formed thereon and a specific pattern is drawn on the resist film by drawing light (laser light) of a drawing device (for example, a laser drawing device). The reflection of the front side of the film 12 can improve the CD Uniformity of the resist pattern and the mask pattern formed based on it. In addition, when the second reflection suppression layer 15 is used as a photomask, it is arranged on the side of the substrate for the display device as the transfer object, and can suppress the light reflected by the transfer object from the front surface of the light-shielding film 12 of the photomask The side reflects again and returns to the transferred body to prevent the deterioration of the transferred image and contribute to the improvement of the transfer characteristics. It can also suppress the display caused by the exposure light above the assumed exposure near the overlap of the display device substrate The generation of inequality.

(遮光膜之材料) 繼而，對遮光膜12中之各層之材料進行說明。 第1反射抑制層13係由含有鉻、氧及氮之鉻系材料而構成。第1反射抑制層13中之氧發揮降低來自背面側之曝光光之反射率之效果。又，第1反射抑制層13中之氮除了發揮降低來自背面側之曝光光之反射率之效果以外，還發揮令使用光罩基底藉由蝕刻(尤其濕式蝕刻)而形成之遮光膜圖案之剖面接近垂直，並且提高CD均勻性之效果。再者，自控制蝕刻特性之視點而言，亦可進而含有碳或氟。 遮光層14由含有鉻及氮之鉻系材料而構成。遮光層14中之氮發揮如下效果，使與第1反射抑制層13、第2反射抑制層15之蝕刻速率差變小且令使用光罩基底藉由蝕刻(尤其濕式蝕刻)而形成之遮光膜圖案之剖面接近垂直，並且使遮光膜12(整體)中之蝕刻時間縮短，提高CD均勻性。再者，自控制蝕刻特性之視點而言，亦可進而含有氧、碳、氟。 第2反射抑制層15係由含有鉻、氧及氮之鉻系材料而構成。第2反射抑制層15中之氧發揮降低來自正面側之描畫裝置之描畫光之反射率或來自正面側之曝光光之反射率的效果。又，發揮提高與抗蝕劑膜之密接性，由來自抗蝕劑膜與遮光膜12之界面之蝕刻劑之滲透所致之側蝕刻抑制的效果。又，第2反射抑制層15中之氮除了發揮降低來自正面側之描畫光之反射率、來自正面側之曝光光之反射率之效果以外，還發揮令使用光罩基底藉由蝕刻(尤其濕式蝕刻)而形成之遮光膜圖案之剖面接近垂直，並且提高CD均勻性之效果。再者，自控制蝕刻特性之視點而言，亦可進而含有碳或氟。(Material of shading film) Next, the materials of each layer in the light-shielding film 12 will be described. The first reflection suppression layer 13 is composed of a chromium-based material containing chromium, oxygen, and nitrogen. The oxygen in the first reflection suppression layer 13 has an effect of reducing the reflectance of the exposure light from the back side. In addition, the nitrogen in the first reflection suppression layer 13 not only exhibits the effect of reducing the reflectivity of the exposure light from the back side, but also plays a role in the light-shielding film pattern formed by etching (especially wet etching) using a photomask substrate. The profile is close to vertical, and the effect of improving CD uniformity. Furthermore, from the viewpoint of controlling the etching characteristics, carbon or fluorine may be further contained. The light shielding layer 14 is made of a chromium-based material containing chromium and nitrogen. The nitrogen in the light-shielding layer 14 exerts the following effects to reduce the difference in the etching rate with the first reflection-inhibiting layer 13 and the second reflection-inhibiting layer 15 and to make the light shielding formed by etching (especially wet etching) using the mask substrate The cross-section of the film pattern is close to vertical, and the etching time in the light-shielding film 12 (overall) is shortened, and the CD uniformity is improved. Furthermore, from the viewpoint of controlling the etching characteristics, oxygen, carbon, and fluorine may be further contained. The second reflection suppression layer 15 is composed of a chromium-based material containing chromium, oxygen, and nitrogen. The oxygen in the second reflection suppression layer 15 has an effect of reducing the reflectivity of the drawing light from the drawing device on the front side or the reflectivity of the exposure light from the front side. In addition, it exerts an effect of improving the adhesion to the resist film and suppressing side etching due to the penetration of the etchant from the interface between the resist film and the light-shielding film 12. In addition, the nitrogen in the second reflection suppression layer 15 not only has the effect of reducing the reflectivity of the drawing light from the front side and the reflectivity of the exposure light from the front side, but also has the effect of making use of the photomask substrate by etching (especially wet The cross-section of the light-shielding film pattern formed by etching) is close to vertical, and the effect of improving the uniformity of CD. Furthermore, from the viewpoint of controlling the etching characteristics, carbon or fluorine may be further contained.

(遮光膜之組成) 繼而，對遮光膜12中之各層之組成進行說明。再者，下述各元素之含有率設為藉由X射線光電分光法(XPS)而測定出之值。(Composition of shading film) Next, the composition of each layer in the light-shielding film 12 will be described. In addition, the content rate of each of the following elements shall be the value measured by X-ray photoelectric spectroscopy (XPS).

遮光膜12係以如下方式構成，即，第1反射抑制層13以含有率計分別包含25～75原子%之鉻(Cr)、15～45原子%之氧(O)、10～30原子%之氮(N)，遮光層14以含有率計分別包含70～95原子%之鉻(Cr)、5～30原子%之氮(N)，第2反射抑制層15以含有率計分別包含30～75原子%之鉻(Cr)、20～50原子%之氧(O)、5～20原子%之氮(N)。較佳為，第1反射抑制層13以含有率計分別包含50～75原子%之Cr、15～35原子%之O、10～25原子%之N，第2反射抑制層15以含有率計分別包含50～75原子%之Cr，20～40原子%之O、5～20原子%之N。The light-shielding film 12 is configured in such a way that the first reflection suppression layer 13 contains 25 to 75 atomic% of chromium (Cr), 15 to 45 atomic% of oxygen (O), and 10 to 30 atomic% in terms of content. The light-shielding layer 14 contains 70 to 95 atomic% of chromium (Cr) and 5 to 30 atomic% of nitrogen (N) in terms of content, and the second reflection suppression layer 15 contains 30 to 30 ～75 atomic% of chromium (Cr), 20-50 atomic% of oxygen (O), 5-20 atomic% of nitrogen (N). Preferably, the first reflection suppressing layer 13 contains 50 to 75 atomic% of Cr, 15 to 35 atomic% of O, and 10 to 25 atomic% of N, respectively, in terms of content rate, and the second reflection inhibiting layer 15 is calculated in terms of content rate. They respectively contain 50 to 75 atomic% of Cr, 20 to 40 atomic% of O, and 5 to 20 atomic% of N.

較佳為，第1反射抑制層13及第2反射抑制層15分別具有O及N中至少任一個元素之含有率沿著膜厚方向而連續地或階段性地發生組成變化之區域。Preferably, the first reflection suppression layer 13 and the second reflection suppression layer 15 each have a region where the content of at least one of O and N elements continuously or stepwise changes in composition along the film thickness direction.

較佳為，第2反射抑制層15具有朝向膜厚方向之遮光層14側而O含有率(氧之含有率)增加之區域。Preferably, the second reflection suppression layer 15 has a region where the O content rate (oxygen content rate) increases toward the light-shielding layer 14 side in the film thickness direction.

又，較佳為，第2反射抑制層15具有朝向膜厚方向之遮光層14側而N含有率(氮之含有率)降低之區域。Furthermore, it is preferable that the second reflection suppression layer 15 has a region where the N content (nitrogen content) decreases toward the light-shielding layer 14 side in the film thickness direction.

又，較佳為，第1反射抑制層13具有朝向膜厚方向之透明基板11而O含有率增加並且N含有率降低之區域。Furthermore, it is preferable that the first reflection suppression layer 13 has a region in which the O content increases and the N content decreases in the transparent substrate 11 facing the film thickness direction.

又，於光罩基底1及由其製作之光罩中，自進一步降低遮光膜12或遮光膜圖案之正背面之反射率，使該等之反射率之差變小之觀點而言，較佳為，以第2反射抑制層15較第1反射抑制層13而言O含有率變高之方式構成，較佳為，以第1反射抑制層13較第2反射抑制層15而言N含有率變高之方式構成。具體而言，較佳為，使第2反射抑制層15之O含有率較第1反射抑制層13大5原子%以上，進而較佳為大10原子%以上較佳。進而，較佳為，使第1反射抑制層13之N含有率較第2反射抑制層15大5原子%以上，進而較佳為大10原子%以上較佳。再者，若於第1反射抑制層13或第2反射抑制層15具有組成傾斜區域之情形時，則其O含有率或N含有率表示膜厚方向上之平均的濃度。Moreover, in the photomask substrate 1 and the photomask made therefrom, it is preferable to further reduce the reflectance of the front and back surfaces of the light-shielding film 12 or the light-shielding film pattern, so as to reduce the difference in reflectivity. In order to configure the second reflection suppression layer 15 to have a higher O content rate than the first reflection suppression layer 13, it is preferable that the first reflection suppression layer 13 has an N content rate compared to the second reflection suppression layer 15 The way to become taller. Specifically, it is preferable that the O content of the second reflection suppression layer 15 is greater than that of the first reflection suppression layer 13 by 5 atomic% or more, and more preferably 10 atomic% or more. Furthermore, it is preferable that the N content of the first reflection suppression layer 13 is greater than that of the second reflection suppression layer 15 by 5 atomic% or more, and more preferably 10 atomic% or more. In addition, when the first reflection suppression layer 13 or the second reflection suppression layer 15 has a compositionally inclined region, the O content rate or the N content rate represents the average concentration in the film thickness direction.

又，於第1反射抑制層13、遮光層14及第2反射抑制層15中，各元素之含有率之變化可為連續性或階段性，但較佳為連續性。In addition, in the first reflection suppression layer 13, the light shielding layer 14, and the second reflection suppression layer 15, the change in the content rate of each element may be continuous or stepwise, but it is preferably continuous.

(關於鍵結狀態(化學狀態)) 較佳為，遮光層14包含鉻(Cr)與氮化二鉻(Cr2 N)。 較佳為，第1反射抑制層13、第2反射抑制層15包含氮化鉻(CrN)、氧化鉻(III)(Cr2 O3 )及氧化鉻(VI)(CrO3 )。(Regarding the bonding state (chemical state)) Preferably, the light shielding layer 14 contains chromium (Cr) and chromium nitride (Cr 2 N). Preferably, the first reflection suppression layer 13 and the second reflection suppression layer 15 include chromium nitride (CrN), chromium (III) oxide (Cr 2 O 3 ), and chromium (VI) oxide (CrO 3 ).

(關於膜厚) 於遮光膜12中，第1反射抑制層13、遮光層14及第2反射抑制層15之各自之厚度並不特別限定，可根據遮光膜12所要求之光學濃度或反射率而適當調整。第1反射抑制層13之厚度只要為如相對於來自遮光膜12之背面側之光，發揮由第1反射抑制層13之正面之反射與第1反射抑制層13及遮光層14之界面之反射所致之光干涉效果的厚度即可。另一方面，第2反射抑制層15之厚度只要為如相對於來自遮光膜12之正面側之光，發揮由第2反射抑制層15之正面之反射與第2反射抑制層15及遮光層14之界面之反射所致之光干涉效果的厚度即可。遮光層14之厚度只要為如遮光膜12之光學濃度成為3以上之厚度即可。具體而言，自於遮光膜12中使正背面之相對於曝光波長之反射率為10%以下，且使光學濃度為3.0以上之觀點而言，例如，可使第1反射抑制層13之膜厚為15 nm～60 nm，使遮光層14之膜厚為50 nm～120 nm，使第2反射抑制層15之膜厚為10 nm～60 nm。(About film thickness) In the light-shielding film 12, the respective thicknesses of the first reflection-inhibiting layer 13, the light-shielding layer 14 and the second reflection-inhibiting layer 15 are not particularly limited, and can be appropriately adjusted according to the optical density or reflectance required by the light-shielding film 12. The thickness of the first reflection suppression layer 13 should be such as to exhibit reflection from the front surface of the first reflection suppression layer 13 and the interface between the first reflection suppression layer 13 and the light shielding layer 14 with respect to the light from the back side of the light shielding film 12 The thickness of the resulting light interference effect is sufficient. On the other hand, the thickness of the second reflection suppression layer 15 needs to be such that the light from the front side of the light-shielding film 12 can be used for the reflection from the front surface of the second reflection suppression layer 15 and the second reflection suppression layer 15 and the light-shielding layer 14 The thickness of the light interference effect caused by the reflection of the interface is sufficient. The thickness of the light-shielding layer 14 may be such that the optical density of the light-shielding film 12 is 3 or more. Specifically, from the viewpoint of making the reflectance of the front and back surfaces with respect to the exposure wavelength to be 10% or less in the light-shielding film 12, and the optical density to be 3.0 or more, for example, the film of the first reflection suppression layer 13 can be made The thickness is 15 nm to 60 nm, the film thickness of the light shielding layer 14 is 50 nm to 120 nm, and the film thickness of the second reflection suppression layer 15 is 10 nm to 60 nm.

＜光罩基底之製造方法＞ 繼而，對上述光罩基底1之製造方法進行說明。＜Manufacturing method of mask substrate＞ Next, the manufacturing method of the above-mentioned photomask substrate 1 is demonstrated.

(準備步驟) 準備相對於曝光光實質上透明之透明基板11。再者，可根據需要而實施研削步驟、研磨步驟等任意之加工步驟，以使透明基板11成為平坦且平滑之主表面。於研磨後，可進行洗淨而將透明基板11之正面之異物或污染去除。作為洗淨，例如，可使用硫酸、硫酸過氧化氫混合物(SPM)、氨、氨水過氧化氫混合物(APM)、OH自由基洗淨水、臭氧水、溫水等。(Preparatory steps) A transparent substrate 11 that is substantially transparent to exposure light is prepared. Furthermore, arbitrary processing steps such as a grinding step and a polishing step may be implemented as needed to make the transparent substrate 11 a flat and smooth main surface. After polishing, cleaning can be performed to remove foreign matter or contamination on the front surface of the transparent substrate 11. As washing, for example, sulfuric acid, sulfuric acid hydrogen peroxide mixture (SPM), ammonia, ammonia water hydrogen peroxide mixture (APM), OH radical washing water, ozone water, warm water, etc. can be used.

(第1反射抑制層之形成步驟) 繼而，於透明基板11上形成第1反射抑制層13。該形成係藉由使用含有Cr之濺鍍靶、以及包含氧系氣體、氮系氣體之反應性氣體及包含稀有氣體之濺鍍氣體之反應性濺鍍而進行成膜。此時，作為成膜條件，濺鍍氣體中所包含之反應性氣體之流量係選擇成為金屬模式之流量。(Steps of forming the first reflection suppression layer) Then, the first reflection suppression layer 13 is formed on the transparent substrate 11. The formation is performed by reactive sputtering using a sputtering target containing Cr, a reactive gas containing oxygen-based gas, nitrogen-based gas, and a sputtering gas containing rare gas. At this time, as the film forming condition, the flow rate of the reactive gas contained in the sputtering gas is selected to be the flow rate of the metal mode.

此處，使用圖5對金屬模式進行說明。圖5係用以說明利用反應性濺鍍形成薄膜之情形時之成膜模式之模式圖，橫軸表示稀有氣體與反應性氣體之混合氣體中之反應性氣體之分壓(流量)比率，縱軸表示施加至靶之電壓。於反應性濺鍍中，於一面導入氧系氣體或氮系氣體等反應性氣體一面使靶放電時，放電電漿之狀態根據反應性氣體之流量而變化，隨之，成膜速度變化。根據該成膜速度之差異有3個模式。具體而言，如圖5所示，有使反應性氣體之供給量(比率)大於某閾值之反應模式、使反應性氣體之供給量(比率)少於反應模式之金屬模式、以及使反應性氣體之供給量(比率)設定於反應模式與金屬模式之間的過渡模式。於金屬模式中，藉由使反應性氣體之比率變少，而使反應性氣體向靶表面之附著變少，可使成膜速度變快。而且，於金屬模式中，由於反應性氣體之供給量較少，故而，例如，可形成較具有化學計量組成之膜而O濃度(氧濃度)或N濃度(氮濃度)之至少任一者之濃度變低的膜。即，可形成Cr之含有率相對性地多，O含有率或N含有率較低之膜。Here, the metal mode will be described using FIG. 5. Fig. 5 is a schematic diagram for explaining the film formation mode in the case of forming a thin film by reactive sputtering. The horizontal axis represents the partial pressure (flow rate) ratio of the reactive gas in the mixed gas of the rare gas and the reactive gas, vertical The axis represents the voltage applied to the target. In reactive sputtering, when a target is discharged while introducing a reactive gas such as an oxygen-based gas or a nitrogen-based gas, the state of the discharge plasma changes according to the flow rate of the reactive gas, and accordingly, the film formation rate changes. There are 3 modes based on the difference in film formation speed. Specifically, as shown in FIG. 5, there are a reaction mode in which the supply amount (ratio) of the reactive gas is greater than a certain threshold, a metal mode in which the supply amount (ratio) of the reactive gas is less than the reaction mode, and a metal mode that makes the reactive gas The gas supply amount (ratio) is set in the transition mode between the reaction mode and the metal mode. In the metal mode, by reducing the ratio of the reactive gas, the adhesion of the reactive gas to the target surface is reduced, and the film formation speed can be increased. Moreover, in the metal mode, since the supply amount of the reactive gas is small, for example, a film having a relatively stoichiometric composition can be formed and at least one of O concentration (oxygen concentration) or N concentration (nitrogen concentration) can be formed. Film with lower concentration. That is, it is possible to form a film having a relatively high Cr content and a low O content or N content.

作為用以成膜第1反射抑制層13之金屬模式之條件，例如，可使氧系氣體之流量為5～45 sccm，使氮系氣體之流量為30～60 sccm，使稀有氣體之流量為60～150 sccm。又，可將靶施加電力設為2.0～6.0 kW，將靶之施加電壓設為420～430 V。As the conditions of the metal mode for forming the first reflection suppression layer 13, for example, the flow rate of the oxygen-based gas may be 5 to 45 sccm, the flow rate of the nitrogen-based gas may be 30-60 sccm, and the flow rate of the rare gas may be 60～150 sccm. In addition, the target applied power can be set to 2.0 to 6.0 kW, and the target applied voltage can be set to 420 to 430 V.

作為濺鍍靶，只要含有Cr即可，例如，除了鉻金屬以外，可使用氧化鉻、氮化鉻、氮氧化鉻等鉻系材料。作為氧系氣體，例如，可使用氧(O2 )、二氧化碳(CO2 )、氮氧化物氣體(N2 O、NO、NO2 )等。其中，自氧化力較高之情況而言，較佳為使用氧(O2 )氣體。又，作為氮系氣體，可使用氮(N2 )等。作為稀有氣體，例如，亦可使用氦氣、氖氣、氬氣、氪氣及氙氣等。再者，除了上述反應性氣體以外，亦可供給烴系氣體，例如可使用甲烷氣體或丁烷氣體等。As the sputtering target, it is sufficient to contain Cr. For example, in addition to chromium metal, chromium-based materials such as chromium oxide, chromium nitride, and chromium oxynitride can be used. As the oxygen-based gas, for example, oxygen (O 2 ), carbon dioxide (CO 2 ), nitrogen oxide gas (N 2 O, NO, NO 2 ), or the like can be used. Among them, when the self-oxidizing power is high, it is preferable to use oxygen (O 2 ) gas. In addition, as the nitrogen-based gas, nitrogen (N 2 ) or the like can be used. As the rare gas, for example, helium, neon, argon, krypton, xenon, etc. may also be used. Furthermore, in addition to the above-mentioned reactive gas, a hydrocarbon-based gas may be supplied. For example, methane gas or butane gas may be used.

於本實施形態中，將反應性氣體之流量及濺鍍靶施加電力設定為如成為金屬模式之條件，使用含有Cr之濺鍍靶，藉由反應性濺鍍而進行成膜處理，藉此，於透明基板11上形成以含有率計包含25～75原子%之Cr、15～45原子%之O、10～30原子%之N之第1反射抑制層13。In this embodiment, the flow rate of the reactive gas and the power applied to the sputtering target are set to the conditions such as the metal mode, and the sputtering target containing Cr is used to perform the film forming process by reactive sputtering, thereby, A first reflection suppression layer 13 containing 25 to 75 atomic% of Cr, 15 to 45 atomic% of O, and 10 to 30 atomic% of N in terms of content is formed on the transparent substrate 11.

再者，於將第1反射抑制層13形成為於膜厚方向上組成均勻之單一膜之情形時，只要不改變反應性氣體之種類或流量地成膜即可，但於以在膜厚方向上O含有率或N含有率變化之方式發生組成傾斜之情形時，可適當變更反應性氣體之種類或流量、反應性氣體中之氧系氣體或氮系氣體之比率等。又，亦可變更氣體供給口之配置或氣體供給方法等。Furthermore, when the first reflection suppression layer 13 is formed as a single film with a uniform composition in the film thickness direction, the film may be formed without changing the type or flow rate of the reactive gas. When the composition is inclined due to the change of the upper O content rate or the N content rate, the type or flow rate of the reactive gas, the ratio of the oxygen-based gas or the nitrogen-based gas in the reactive gas, etc. can be appropriately changed. In addition, it is also possible to change the arrangement of the gas supply port or the gas supply method.

(遮光層之形成步驟) 繼而，於第1反射抑制層13上形成遮光層14。該形成係藉由使用含有之濺鍍靶、及包含氮系氣體與稀有氣體之濺鍍氣體之反應性濺鍍而進行成膜。此時，作為成膜條件，濺鍍氣體中所包含之反應性氣體之流量係選擇成為金屬模式之流量。 作為靶，只要含有即可，例如，除了鉻金屬以外，可使用氧化鉻、氮化鉻、氮氧化鉻等鉻系材料。作為氮系氣體，可使用氮(N2 )等。作為稀有氣體，例如，亦可使用氦氣、氖氣、氬氣、氪氣及氙氣等。再者，除了上述反應性氣體以外，亦可供給上述所說明之氧系氣體、烴系氣體。 於本實施形態中，將反應性氣體之流量及濺鍍靶施加電力設定為如成為金屬模式之條件設定，使用含有之濺鍍靶進行反應性濺鍍，藉此，於第1反射抑制層13上，形成以含有率計包含70～95原子%之Cr、5～30原子%之N之遮光層14。(Step of forming a light-shielding layer) Next, a light-shielding layer 14 is formed on the first reflection suppression layer 13. The formation is performed by reactive sputtering using a sputtering target contained and a sputtering gas containing a nitrogen-based gas and a rare gas. At this time, as the film forming condition, the flow rate of the reactive gas contained in the sputtering gas is selected to be the flow rate of the metal mode. As the target, what is necessary is just to contain, for example, in addition to chromium metal, chromium-based materials, such as chromium oxide, chromium nitride, and chromium oxynitride, can be used. As the nitrogen-based gas, nitrogen (N 2 ) or the like can be used. As the rare gas, for example, helium, neon, argon, krypton, xenon, etc. may also be used. Furthermore, in addition to the above-mentioned reactive gas, the oxygen-based gas and the hydrocarbon-based gas described above may also be supplied. In this embodiment, the flow rate of the reactive gas and the power applied to the sputtering target are set to the condition settings such as the metal mode, and the sputtering target contained therein is used for reactive sputtering, thereby forming the first reflection suppression layer 13 On the top, a light-shielding layer 14 containing 70 to 95 atomic% of Cr and 5 to 30 atomic% of N in terms of content is formed.

再者，作為遮光層14之成膜條件，例如，可使氮系氣體之流量為1～60 sccm，使稀有氣體之流量為60～200 sccm。又，可將靶施加電力設為3.0～7.0 kW，將靶之施加電壓設為370～380 V。Furthermore, as the film formation conditions of the light shielding layer 14, for example, the flow rate of the nitrogen-based gas may be 1 to 60 sccm, and the flow rate of the rare gas may be 60 to 200 sccm. In addition, the target applied power can be set to 3.0 to 7.0 kW, and the target applied voltage can be set to 370 to 380 V.

(第2反射抑制層之形成步驟) 繼而，於遮光層14上形成第2反射抑制層15。該形成係與第1反射抑制層13相同地，將反應性氣體之流量及靶施加電力設定為如成為金屬模式之條件，使用含有之濺鍍靶，藉由反應性濺鍍進行成膜。藉此，於遮光層14上，形成以含有率計包含30～75原子%之Cr、20～50原子%之O、5～20原子%之N之第2反射抑制層15。(Steps of forming the second reflection suppression layer) Then, the second reflection suppression layer 15 is formed on the light shielding layer 14. This formation system is the same as that of the first reflection suppression layer 13, the flow rate of the reactive gas and the target application power are set to the conditions such as the metal mode, and the sputtering target contained therein is used to form a film by reactive sputtering. Thereby, the second reflection suppression layer 15 containing 30 to 75 atomic% of Cr, 20 to 50 atomic% of O, and 5 to 20 atomic% of N in terms of content is formed on the light shielding layer 14.

作為用以成膜第2反射抑制層15之金屬模式之條件，例如，可使氧系氣體之流量為8～45 sccm，使氮系氣體之流量為30～60 sccm，使稀有氣體之流量為60～150 sccm。又，可將靶施加電力設為2.0～6.0 kW，將靶之施加電壓設為420～430 V。As the conditions for the metal mode for forming the second reflection suppression layer 15, for example, the flow rate of the oxygen-based gas may be 8 to 45 sccm, the flow rate of the nitrogen-based gas may be 30-60 sccm, and the flow rate of the rare gas may be 60～150 sccm. In addition, the target applied power can be set to 2.0 to 6.0 kW, and the target applied voltage can be set to 420 to 430 V.

再者，於使第2反射抑制層發生組成傾斜之情形時，如上所述，可適當變更反應性氣體之種類或流量、反應性氣體中之氧系氣體或氮系氣體之比率等。Furthermore, when the composition of the second reflection suppression layer is inclined, as described above, the type or flow rate of the reactive gas, the ratio of the oxygen-based gas or the nitrogen-based gas in the reactive gas, and the like can be appropriately changed.

根據以上，獲得本實施形態之光罩基底1。Based on the above, the mask substrate 1 of this embodiment is obtained.

再者，遮光膜12中之各層之成膜可使用線內型濺鍍裝置利用in-situ進行。於並非線內型濺鍍裝置之情形時，有時於各層之成膜後，必須將透明基板11取出至裝置外，使透明基板11曝露於大氣，各層被表面氧化或表面碳化。其結果，有時使遮光膜12之相對於曝光光之反射率或蝕刻速率變化。因此，若為線內型濺鍍裝置，則不將透明基板11取出至裝置外而曝露於大氣，可連續地成膜各層，故而可抑制未意圖之元素向遮光膜12之取入。Furthermore, the film formation of each layer in the light-shielding film 12 can be performed in-situ using an in-line sputtering device. When it is not an in-line sputtering device, sometimes after the film formation of each layer, the transparent substrate 11 must be taken out of the device to expose the transparent substrate 11 to the atmosphere, and the surface of each layer is oxidized or carbonized. As a result, the reflectance of the light shielding film 12 with respect to the exposure light or the etching rate may be changed. Therefore, if it is an in-line sputtering device, the transparent substrate 11 is not taken out of the device and exposed to the atmosphere, and each layer can be continuously formed. Therefore, the introduction of unintended elements into the light-shielding film 12 can be suppressed.

又，於使用線內型濺鍍裝置成膜遮光膜12之情形時，由於第1反射抑制層13、遮光層14、第2反射抑制層15之各層之間具有連續地發生組成傾斜之組成傾斜區域(過渡層)，故而使用光罩基底藉由蝕刻(尤其濕式蝕刻)而形成之遮光膜圖案之剖面光滑，且可接近垂直，故而較佳。In addition, when the light-shielding film 12 is formed using an in-line sputtering device, the composition of the first reflection-inhibiting layer 13, the light-shielding layer 14, and the second reflection-inhibiting layer 15 has a composition gradient that continuously generates a composition gradient. Area (transition layer), therefore, the cross-section of the light-shielding film pattern formed by etching (especially wet etching) using a mask substrate is smooth and can be close to vertical, so it is preferable.

＜光罩之製造方法＞ 繼而，對使用上述光罩基底1製造光罩之方法進行說明。＜Manufacturing method of photomask＞ Next, a method of manufacturing a photomask using the aforementioned photomask substrate 1 will be described.

(抗蝕劑膜之形成步驟) 首先，於光罩基底1之遮光膜12中之第2反射抑制層15上塗佈抗蝕劑，乾燥後形成抗蝕劑膜。作為抗蝕劑，必須根據所使用之描畫裝置選擇適當者，可使用正型或負型抗蝕劑。(Steps of forming resist film) First, a resist is coated on the second reflection suppression layer 15 in the light-shielding film 12 of the photomask base 1, and a resist film is formed after drying. As the resist, an appropriate one must be selected according to the drawing device used, and either a positive type or a negative type resist can be used.

(抗蝕劑圖案之形成步驟) 繼而，使用描畫裝置於抗蝕劑膜描畫特定圖案。通常，於製作顯示裝置製造用之光罩時，使用雷射描畫裝置。於描畫後，藉由對抗蝕劑膜實施顯影及沖洗，而形成特定之抗蝕劑圖案。(Steps of forming resist pattern) Then, a drawing device is used to draw a specific pattern on the resist film. Generally, a laser drawing device is used when manufacturing a mask for manufacturing a display device. After drawing, the resist film is developed and rinsed to form a specific resist pattern.

於本實施形態中，由於以使第2反射抑制層15之反射率變低之方式構成，故而於在抗蝕劑膜描畫圖案時，可使描畫光(雷射光)之反射變少。藉此，可形成圖案精度較高之抗蝕劑圖案，隨之，可形成尺寸精度較高之遮罩圖案。In this embodiment, since the reflectance of the second reflection suppression layer 15 is lowered, it is possible to reduce the reflection of the drawing light (laser light) when the pattern is drawn on the resist film. Thereby, a resist pattern with higher pattern accuracy can be formed, and accordingly, a mask pattern with higher dimensional accuracy can be formed.

(遮罩圖案之形成步驟) 繼而，藉由將抗蝕劑圖案作為遮罩對遮光膜12進行蝕刻，而形成由遮光膜圖案構成之遮罩圖案。蝕刻既可為濕式蝕刻亦可為乾式蝕刻。通常，於顯示裝置製造用之光罩中，進行濕式蝕刻，作為濕式蝕刻中所使用之蝕刻液(蝕刻劑)，例如，可使用包含硝酸鈰銨與過氯酸之鉻蝕刻液。(Steps of forming mask pattern) Then, the light-shielding film 12 is etched by using the resist pattern as a mask to form a mask pattern composed of the light-shielding film pattern. The etching can be either wet etching or dry etching. Generally, wet etching is performed in a photomask for manufacturing a display device. As an etching solution (etchant) used in wet etching, for example, a chromium etching solution containing cerium ammonium nitrate and perchloric acid can be used.

於本實施形態中，由於在遮光膜12之厚度方向，以第1反射抑制層13、遮光層14及第2反射抑制層15之蝕刻速率一致之方式調整各層之組成，故而可使濕式蝕刻後之剖面形狀即遮光膜圖案(遮罩圖案)之剖面形狀相對於透明基板11接近垂直，可獲得較高之CD均勻性(CD Uniformity)。In this embodiment, the composition of each layer is adjusted so that the etching rates of the first reflection suppression layer 13, the light blocking layer 14, and the second reflection suppression layer 15 are the same in the thickness direction of the light-shielding film 12, so that wet etching can be achieved. The latter cross-sectional shape, that is, the cross-sectional shape of the light-shielding film pattern (mask pattern) is close to perpendicular to the transparent substrate 11, and a higher CD uniformity (CD Uniformity) can be obtained.

(剝離步驟) 繼而，將抗蝕劑圖案剝離，獲得於透明基板11上形成有遮光膜圖案(遮罩圖案)之光罩。(Peeling step) Then, the resist pattern is peeled off, and a photomask having a light-shielding film pattern (mask pattern) formed on the transparent substrate 11 is obtained.

根據以上，獲得本實施形態之光罩。Based on the above, the photomask of this embodiment is obtained.

＜顯示裝置之製造方法＞ 繼而，對使用上述光罩製造顯示裝置之方法進行說明。＜Manufacturing method of display device＞ Next, a method of manufacturing a display device using the above-mentioned photomask will be described.

(準備步驟) 首先，對在顯示裝置之基板上形成有抗蝕劑膜之帶抗蝕劑膜之基板，將藉由上述光罩之製造方法而獲得之光罩以與介隔曝光裝置之投影光學系統而形成於基板上之抗蝕劑膜對向之配置方式，載置於曝光裝置之遮罩載台上。(Preparatory steps) First, for a substrate with a resist film on which a resist film is formed on the substrate of a display device, the photomask obtained by the above-mentioned photomask manufacturing method is formed by separating the projection optical system of the exposure device The resist film on the substrate is placed on the mask stage of the exposure device.

(曝光步驟(圖案轉印步驟)) 其次，進行抗蝕劑曝光步驟，即，將曝光光照射至光罩，將圖案轉印至形成於顯示裝置之基板上之抗蝕劑膜。 曝光光例如使用自300 nm～550 nm之波長區域選擇之單波長之光(j射線(波長313 nm)、i射線(波長365 nm)、h射線(波長405 nm)、g射線(波長436 nm)等)、或包含複數個波長之光(例如，j射線(波長313 nm)、i射線(波長365 nm)、h射線(405 nm)、g射線(波長436 nm))之複合光。於本實施形態中，由於使用遮光膜圖案(遮罩圖案)之正背面之反射率降低之光罩製造顯示裝置(顯示面板)，故而可獲得無顯示不均之顯示裝置(顯示面板)。(Exposure step (pattern transfer step)) Next, a resist exposure step is performed, that is, exposure light is irradiated to the photomask, and the pattern is transferred to the resist film formed on the substrate of the display device. The exposure light uses, for example, single-wavelength light (j-ray (wavelength 313 nm), i-ray (wavelength 365 nm), h-ray (wavelength 405 nm), g-ray (wavelength 436 nm) selected from the wavelength region of 300 nm to 550 nm. ), etc.), or composite light containing multiple wavelengths of light (for example, j-ray (wavelength 313 nm), i-ray (wavelength 365 nm), h-ray (405 nm), g-ray (wavelength 436 nm)). In the present embodiment, since the light-shielding film pattern (mask pattern) is used to manufacture a display device (display panel) with a reduced reflectivity on the front and back surfaces, a display device (display panel) without display unevenness can be obtained.

＜本實施形態之效果＞ 根據本實施形態，發揮以下所示之1個或複數個效果。<Effects of this embodiment> According to this embodiment, one or more effects shown below are exhibited.

(a)本實施形態之光罩基底1係以如下方式構成，即，使第1反射抑制層13、遮光層14及第2反射抑制層15積層而形成遮光膜12，第1反射抑制層13係含有鉻、氧及氮之鉻系材料，且具有Cr含有率為25～75原子%、O含有率為15～45原子%、N含有率為10～30原子%之組成，遮光層14係含有鉻及氮之鉻系材料，且具有Cr含有率為70～95原子%、N含有率為5～30原子%之組成，第2反射抑制層15係含有鉻、氧及氮之鉻系材料，且具有Cr含有率為30～75原子%、O含有率為20～50原子%、N含有率為5～20原子%之組成。而且，使第1反射抑制層13及第2反射抑制層15之厚度為如最大限或接近最大限地獲得光干涉效果之厚度。藉此，可使光罩基底1之正背面之相對於曝光波長之反射率降低，分別設為10%以下。具體而言，於正背面之反射率光譜中，可使反射率極小之底部峰值之波長為相對高波長側之380 nm～480 nm，使波長380 nm～480 nm之光之反射率為10%以下，較佳為7.5%以下。另一方面，藉由使遮光層14為特定厚度，可使遮光膜12中之光學濃度為3.0以上。(a) The mask base 1 of the present embodiment is constructed in such a way that the first reflection suppression layer 13, the light shielding layer 14, and the second reflection suppression layer 15 are laminated to form the light shielding film 12, and the first reflection suppression layer 13 It is a chromium-based material containing chromium, oxygen and nitrogen, and has a composition with a Cr content of 25 to 75 atomic %, an O content of 15 to 45 atomic %, and a N content of 10 to 30 atomic %. The light-shielding layer 14 A chromium-based material containing chromium and nitrogen, with a Cr content of 70 to 95 atomic% and a N content of 5 to 30 atomic%. The second reflection suppression layer 15 is a chromium-based material containing chromium, oxygen and nitrogen , And has a composition in which the Cr content is 30 to 75 atomic %, the O content is 20 to 50 atomic %, and the N content is 5 to 20 atomic %. In addition, the thickness of the first reflection suppression layer 13 and the second reflection suppression layer 15 is set to the maximum or close to the maximum to obtain the optical interference effect. As a result, the reflectance of the front and back surfaces of the photomask substrate 1 with respect to the exposure wavelength can be reduced to 10% or less, respectively. Specifically, in the reflectance spectrum of the front and back sides, the wavelength of the bottom peak with the lowest reflectance can be made 380 nm～480 nm on the relatively high wavelength side, so that the reflectance of light with a wavelength of 380 nm～480 nm is 10% Below, it is preferably 7.5% or less. On the other hand, by setting the light-shielding layer 14 to a specific thickness, the optical density in the light-shielding film 12 can be made 3.0 or more.

(b)又，於本實施形態中，藉由使第1反射抑制層13及第2反射抑制層15之組成於上述範圍內適當變更，可分別調整光罩基底1之背面側(透明基板11側)之反射率、及正面側(遮光膜12側)之反射率。例如，可將光罩基底1之反射率以正面側較背面側高之方式、以正面側與背面側相同之方式、或者以背面側較正面側高之方式分別調整。再者，於使用已製作之光罩對被轉印體進行曝光處理時，自抑制由曝光光自光罩向光源側之反射所致之影響(重影之產生等)之觀點而言，較佳為，使背面側之反射率較正面側高。換言之，較佳為，使光罩基底1之正面側(遮光膜12側)之反射率較背面側(透明基板11側)之反射率低。具體而言，於將TFT(thin-film transistor，薄膜電晶體)陣列中之閘極電極或源極電極/汲極電極之配線圖案轉印至形成於作為被轉印體之顯示裝置之基板上之抗蝕劑膜時，光罩之遮光膜圖案之開口率成為50%以上，故而通過光罩之曝光光量變高，故而容易因來自被轉印體側之曝光光之返回光而產生眩光。因此，藉由使光罩基底1之遮光膜12之正面及背面之相對於曝光波長之反射率分別為10%以下，且使遮光膜12之正面側之反射率較背面側之反射率低，可降低眩光之影響，可防止使用光罩製作顯示裝置時之CD誤差。(b) In this embodiment, by appropriately changing the composition of the first reflection suppression layer 13 and the second reflection suppression layer 15 within the above range, the back side of the mask base 1 (transparent substrate 11 The reflectance of the side) and the reflectance of the front side (the light-shielding film 12 side). For example, the reflectance of the mask substrate 1 can be adjusted so that the front side is higher than the back side, the front side is the same as the back side, or the back side is higher than the front side. Furthermore, when using a manufactured photomask to expose the transferred body, it is more effective from the viewpoint of suppressing the influence caused by the reflection of the exposure light from the photomask to the light source side (ghosting, etc.) Preferably, the reflectance on the back side is higher than that on the front side. In other words, it is preferable to make the reflectance of the front side (the light shielding film 12 side) of the mask base 1 lower than the reflectance of the back side (the transparent substrate 11 side). Specifically, the wiring pattern of the gate electrode or the source electrode/drain electrode in the TFT (thin-film transistor) array is transferred to the substrate formed on the display device as the transferred body In the case of the resist film, the aperture ratio of the light-shielding film pattern of the mask becomes more than 50%, so the amount of exposure light passing through the mask becomes higher, so it is easy to generate glare due to the return light of the exposure light from the side of the transferred body. Therefore, by making the reflectance of the front and back of the light-shielding film 12 of the mask substrate 1 with respect to the exposure wavelength to be 10% or less, and the reflectance of the front side of the light-shielding film 12 is lower than the reflectance of the back side, It can reduce the effect of glare and prevent CD errors when using photomasks to make display devices.

(c)又，於本實施形態中，藉由使構成遮光膜12之第1反射抑制層13、遮光層14、第2反射抑制層15之各層為上述組成範圍，可降低使蝕刻速率降低之O或使蝕刻速率增加之N之濃度，抑制各層之蝕刻速率之差。藉此，可使蝕刻光罩基底1之遮光膜12時之剖面形狀即遮罩圖案之剖面形狀相對於透明基板11接近垂直。具體而言，於遮罩圖案之剖面形狀中，於將藉由蝕刻而形成之側面與透明基板11所成之角設為Θ時，可使Θ為90°±30°之範圍內。又，可使遮罩圖案之剖面形狀接近垂直，並且可抑制第1反射抑制層13之蝕刻殘留，或第1反射抑制層13及第2反射抑制層15之被侵蝕(所謂底切)、側蝕刻等。其結果，可提高遮罩圖案(遮光膜圖案)中之CD均勻性，可形成100 nm以下之高精度之遮罩圖案。(c) In this embodiment, the first reflection suppression layer 13, the light blocking layer 14, and the second reflection suppression layer 15 constituting the light-shielding film 12 are in the above composition range, so that the etching rate can be reduced. The concentration of O or N, which increases the etching rate, suppresses the difference in the etching rate of each layer. Thereby, the cross-sectional shape of the mask pattern when the light-shielding film 12 of the photomask base 1 is etched can be made close to perpendicular to the transparent substrate 11. Specifically, in the cross-sectional shape of the mask pattern, when the angle formed by the side surface formed by etching and the transparent substrate 11 is set to Θ, Θ can be made within the range of 90°±30°. In addition, the cross-sectional shape of the mask pattern can be made close to vertical, and the etching residue of the first reflection suppression layer 13 or the erosion (so-called undercut) of the first reflection suppression layer 13 and the second reflection suppression layer 15 can be suppressed. Etching etc. As a result, the CD uniformity in the mask pattern (light-shielding film pattern) can be improved, and a high-precision mask pattern below 100 nm can be formed.

(d)又，於本實施形態中，遮光膜12係藉由使構成遮光膜12之第1反射抑制層13、遮光層14、第2反射抑制層15之各層之蝕刻速率一致，而無論蝕刻時間之長短或蝕刻液之濃淡、蝕刻液之溫度如何，均可穩定地確保剖面形狀之垂直性。例如，於將遮光膜12之恰蝕刻時間設為T時，即便於使蝕刻時間為1.5×T而進行過蝕刻之情形時，亦可獲得與使蝕刻時間為T之情形時同等之垂直性。具體而言，可將使蝕刻時間為T時之遮光膜圖案之剖面所成之角度Θ1與使蝕刻時間為1.5×T而進行過蝕刻後之剖面所成之角度Θ2的差設為10°以下。又，同樣地，於使蝕刻液之濃度變高之情形時與使蝕刻液之濃度變低之情形時，可將遮光膜圖案之剖面所成之角之差設為10°以下。又，同樣地，於使蝕刻液之溫度變高之情形時(例如42℃)與使蝕刻液之溫度變低之情形時(例如室溫23℃)，蝕刻液之溫度越高則蝕刻速率越高，但可將遮光膜圖案之剖面所成之角之差設為10°以下。再者，所謂恰蝕刻時間，表示對遮光膜12於膜厚方向蝕刻而使透明基板11之正面開始露出為止之蝕刻時間。(d) In this embodiment, the light-shielding film 12 is formed by making the etching rates of the first reflection-inhibiting layer 13, light-shielding layer 14, and second reflection-inhibiting layer 15 of the light-shielding film 12 uniform regardless of the etching The length of time, the concentration of the etching solution, and the temperature of the etching solution can stably ensure the verticality of the cross-sectional shape. For example, when the just-etching time of the light-shielding film 12 is set to T, even when the etching time is 1.5×T and the over-etching is performed, the same verticality as when the etching time is set to T can be obtained. Specifically, the difference between the angle θ1 formed by the cross-section of the light-shielding film pattern when the etching time is T and the angle θ2 formed by the cross-section after the etching time is 1.5×T can be set to 10° or less . Also, similarly, when the concentration of the etching solution is increased and when the concentration of the etching solution is decreased, the difference in the angle formed by the cross section of the light-shielding film pattern can be 10° or less. Also, similarly, when the temperature of the etching solution is increased (for example, 42°C) and when the temperature of the etching solution is decreased (for example, room temperature 23°C), the higher the temperature of the etching solution, the higher the etching rate. It is high, but the difference in the angle formed by the cross section of the light-shielding film pattern can be 10° or less. In addition, the "just etching time" refers to the etching time until the light-shielding film 12 is etched in the film thickness direction and the front surface of the transparent substrate 11 starts to be exposed.

(e)較佳為，於遮光膜12中，第1反射抑制層13及第2反射抑制層15係含有鉻、氧及氮之鉻系材料，第1反射抑制層13以含有率計分別包含50～75原子%之Cr、15～35原子%之O、10～25原子%之N，第2反射抑制層15以含有率計分別包含50～75原子%之Cr、20～40原子%之O、5～20原子%之N。(e) Preferably, in the light-shielding film 12, the first reflection suppression layer 13 and the second reflection suppression layer 15 are chromium-based materials containing chromium, oxygen, and nitrogen, and the first reflection suppression layer 13 respectively contains 50 to 75 atomic% of Cr, 15 to 35 atomic% of O, 10 to 25 atomic% of N, the second reflection suppression layer 15 contains 50 to 75 atomic% of Cr and 20 to 40 atomic% of O, 5-20 atomic% of N.

於第1反射抑制層13及第2反射抑制層15中，藉由使O含有率進一步降低，可抑制由含有該等之層中之O所致的蝕刻速率之過度增加。因此，以使構成遮光膜12之第1反射抑制層13、遮光層14、第2反射抑制層15之各層之蝕刻速率一致之目的可降低調配於遮光層14之碳(C)之含有率，或者使用遮光層14不含有C而為非含有碳。其結果，可提高遮光層14中之Cr之含有率，將光學濃度(OD)維持得較高。In the first reflection suppression layer 13 and the second reflection suppression layer 15, by further reducing the O content, it is possible to suppress an excessive increase in the etching rate due to O in the layers containing these. Therefore, in order to make the etching rate of each layer of the first reflection suppression layer 13, the light blocking layer 14, and the second reflection suppression layer 15 constituting the light shielding film 12 uniform, the content rate of carbon (C) which is blended in the light shielding layer 14 can be reduced. Alternatively, the light-shielding layer 14 does not contain C but does not contain carbon. As a result, the Cr content in the light shielding layer 14 can be increased, and the optical density (OD) can be maintained high.

另一方面，於第1反射抑制層13及第2反射抑制層15中，藉由使N含有率進一步降低，可抑制由含有該等之層中之N所致的蝕刻速率之過度增加。因此，以使構成遮光膜12之第1反射抑制層13、遮光層14、第2反射抑制層15之各層之蝕刻速率一致之目的可降低遮光層14中含有之N之含有率。其結果，可提高遮光層14中之Cr之含有率，將光學濃度(OD)維持得較高。On the other hand, in the first reflection suppression layer 13 and the second reflection suppression layer 15, by further reducing the N content, it is possible to suppress an excessive increase in the etching rate due to N in the layers containing these. Therefore, the content of N contained in the light-shielding layer 14 can be reduced for the purpose of making the etching rates of the first reflection-inhibiting layer 13, the light-shielding layer 14, and the second reflection-inhibiting layer 15 uniform. As a result, the Cr content in the light shielding layer 14 can be increased, and the optical density (OD) can be maintained high.

(f)較佳為，第1反射抑制層13及第2反射抑制層15分別具有O及N中至少任一個元素之含有率沿著膜厚方向連續地或階段性地發生組成變化之區域。藉由使第1反射抑制層13及第2反射抑制層15之各層發生組成變化，可一面對各層局部地導入O或N成為較高之含有率之區域，一面將各層中之O或N之平均的含有率維持得較低。藉此，可將光罩基底1之正面側及背面側之反射率維持得較低。(f) It is preferable that the first reflection suppression layer 13 and the second reflection suppression layer 15 each have a region where the content of at least one element of O and N changes continuously or stepwise along the film thickness direction. By changing the composition of each layer of the first reflection suppression layer 13 and the second reflection suppression layer 15, it is possible to locally introduce O or N to each layer to become a region with a higher content rate, and to remove the O or N in each layer. The average content rate is maintained low. Thereby, the reflectivity of the front side and the back side of the photomask substrate 1 can be maintained low.

又，於構成遮光膜12之第1反射抑制層13、遮光層14、第2反射抑制層15之各層中，若O含有率變高則蝕刻速率過度地增加，或者若N含有率變高則蝕刻速率過度地增加，藉由使O或N之含有率變低，可抑制由含有該等之元素所致的各層之蝕刻速率之差。即，可抑制第1反射抑制層13及第2反射抑制層15與遮光層14之間之蝕刻速率之背離。其結果，以使構成遮光膜12之第1反射抑制層13、遮光層14、第2反射抑制層15之各層之蝕刻速率一致之目的可使遮光層14中含有之N或碳減少，或者使遮光層14不含有碳而為非含有碳。其結果，可提高遮光層14中之Cr之含有率，將光學濃度(OD)維持得較高。In addition, in each of the first reflection suppression layer 13, the light shielding layer 14, and the second reflection suppression layer 15 constituting the light-shielding film 12, if the O content increases, the etching rate increases excessively, or if the N content increases, The etching rate is excessively increased, and by reducing the content of O or N, the difference in the etching rate of each layer caused by the inclusion of these elements can be suppressed. That is, the deviation of the etching rate between the first reflection suppression layer 13 and the second reflection suppression layer 15 and the light shielding layer 14 can be suppressed. As a result, in order to make the etching rate of each layer of the first reflection suppression layer 13, the light blocking layer 14, and the second reflection suppression layer 15 constituting the light blocking film 12 uniform, the N or carbon contained in the light blocking layer 14 can be reduced, or The light shielding layer 14 does not contain carbon but does not contain carbon. As a result, the Cr content in the light shielding layer 14 can be increased, and the optical density (OD) can be maintained high.

(g)較佳為，第2反射抑制層15具有朝向膜厚方向之遮光層14側而O含有率增加之區域。藉此，於第2反射抑制層15中，使與遮光層14之界面部分之O含有率局部地變高，使膜厚方向上之平均的O含有率變低。其結果，可於遮光膜12之正面側(第2反射抑制層15)獲得所期望之反射率，並且可抑制由界面之過度的蝕刻所致之被侵蝕。(g) It is preferable that the second reflection suppression layer 15 has a region where the O content increases toward the light shielding layer 14 side in the film thickness direction. Thereby, in the second reflection suppression layer 15, the O content in the interface portion with the light shielding layer 14 is locally increased, and the average O content in the film thickness direction is decreased. As a result, a desired reflectance can be obtained on the front side (second reflection suppression layer 15) of the light-shielding film 12, and erosion due to excessive etching of the interface can be suppressed.

(h)較佳為，第2反射抑制層15具有朝向膜厚方向之遮光層14側而N含有率降低之區域。藉此，於第2反射抑制層15中，將膜厚方向上之平均的N含有率維持為某程度，且使與遮光層14之界面部分之N含有率局部地變低。其結果，可抑制由第2反射抑制層15與遮光層14之界面之過度蝕刻所致的被侵蝕。(h) Preferably, the second reflection suppression layer 15 has a region where the N content decreases toward the light-shielding layer 14 side in the film thickness direction. Thereby, in the second reflection suppression layer 15, the average N content in the film thickness direction is maintained at a certain level, and the N content in the interface portion with the light shielding layer 14 is locally lowered. As a result, it is possible to suppress erosion due to excessive etching of the interface between the second reflection suppression layer 15 and the light shielding layer 14.

(i)較佳為，第1反射抑制層13具有朝向膜厚方向之透明基板11而O含有率增加並且N含有率降低之區域。於第1反射抑制層13中，藉由使朝向膜厚方向之透明基板11而O含有率增加並且N含有率降低，可使蝕刻速率朝向透明基板11逐漸變低。藉此，可抑制第1反射抑制層13與透明基板11之界面之被侵蝕，並進一步提高遮罩圖案之CD均勻性。(i) Preferably, the first reflection suppression layer 13 has a region where the O content increases and the N content decreases in the transparent substrate 11 facing the film thickness direction. In the first reflection suppression layer 13, by increasing the O content and decreasing the N content of the transparent substrate 11 in the film thickness direction, the etching rate can be gradually reduced toward the transparent substrate 11. Thereby, the erosion of the interface between the first reflection suppression layer 13 and the transparent substrate 11 can be suppressed, and the CD uniformity of the mask pattern can be further improved.

(j)較佳為，第2反射抑制層15係以較第1反射抑制層13而O含有率變高之方式構成。具體而言，較佳為，第2反射抑制層15之O含有率較第1反射抑制層13大5原子%以上，進而較佳為大10原子%以上較佳。又，第1反射抑制層13係以較第2反射抑制層15而N含有率變高之方式構成。具體而言，較佳為，第1反射抑制層13之N含有率較第2反射抑制層15大5原子%以上，進而較佳為大10原子%以上較佳。根據本發明者們之研究，可知於使第1反射抑制層13及第2反射抑制層15由相同材料形成之情形時，儘管組成相同，但存在正面側之反射率較背面側變高之傾向。因此，對第1反射抑制層13、第2反射抑制層15之各層之組成比(O含有率、N含有率)進行進一步研究，結果發現藉由使第1反射抑制層13及第2反射抑制層15之組成比(O含有率、N含有率)如上所述，可使背面側之反射率與正面側為相同程度，或較正面側降低。藉由如此使各層之組成比(O含有率、N含有率)變更，可控制正背面之反射率。(j) Preferably, the second reflection suppression layer 15 is configured to have a higher O content than the first reflection suppression layer 13. Specifically, it is preferable that the O content of the second reflection suppression layer 15 is greater than that of the first reflection suppression layer 13 by 5 atomic% or more, and more preferably 10 atomic% or more. In addition, the first reflection suppression layer 13 is configured to have a higher N content than the second reflection suppression layer 15. Specifically, it is preferable that the N content of the first reflection suppression layer 13 is greater than that of the second reflection suppression layer 15 by 5 atomic% or more, and more preferably 10 atomic% or more. According to the research conducted by the inventors, when the first reflection suppression layer 13 and the second reflection suppression layer 15 are formed of the same material, although the composition is the same, the reflectance on the front side tends to be higher than that on the back side. . Therefore, the composition ratio (O content rate, N content rate) of each layer of the first reflection suppression layer 13 and the second reflection suppression layer 15 was further studied. As a result, it was found that the first reflection suppression layer 13 and the second reflection suppression layer The composition ratio (O content rate, N content rate) of the layer 15 is as described above, so that the reflectance on the back side can be the same as the front side, or can be lower than the front side. By changing the composition ratio (O content rate, N content rate) of each layer in this way, the reflectance of the front and back surfaces can be controlled.

(k)又，根據本實施形態，較佳為，使遮光層14為包含鉻(Cr)與氮化二鉻(Cr2 N)之鍵結狀態(化學狀態)之鉻系材料。藉由使遮光層14為含有與Cr2 N之鍵結狀態(化學狀態)之鉻系材料，可抑制遮光層14含有特定量之N之情形時之蝕刻速率的過度發展，可使遮光膜圖案之剖面形狀接近垂直。(k) According to this embodiment, the light shielding layer 14 is preferably made of a chromium-based material in a bonding state (chemical state) of chromium (Cr) and chromium nitride (Cr 2 N). By making the light-shielding layer 14 contain a chromium-based material in the bonding state (chemical state) with Cr 2 N, the excessive development of the etching rate when the light-shielding layer 14 contains a specific amount of N can be suppressed, and the pattern of the light-shielding film The cross-sectional shape is close to vertical.

(l)又，根據本實施形態，較佳為，使第1反射抑制層13及第2反射抑制層15為包含氮化鉻(CrN)、氧化鉻(III)(Cr2 O3 )及氧化鉻(VI)(CrO3 )之鍵結狀態(化學狀態)之鉻系材料。藉由使第1反射抑制層13及第2反射抑制層15含有Cr2 O3 、CrO3 之複數個氧化鉻，可有效地降低遮光膜12之正背面之反射率。又，藉由第1反射抑制層13及第2反射抑制層15含有CrN之氮化鉻，可抑制由上述氧化鉻所致的蝕刻速率之過度降低，故而可使遮光膜圖案之剖面形狀接近垂直。(l) According to this embodiment, it is preferable that the first reflection suppression layer 13 and the second reflection suppression layer 15 include chromium nitride (CrN), chromium (III) oxide (Cr 2 O 3 ), and oxide. Chromium (VI) (CrO 3 ) bonding state (chemical state) of chromium-based materials. By making the first reflection suppression layer 13 and the second reflection suppression layer 15 contain plural chromium oxides of Cr 2 O 3 and CrO 3 , the reflectance of the front and back surfaces of the light-shielding film 12 can be effectively reduced. In addition, since the first reflection suppression layer 13 and the second reflection suppression layer 15 contain CrN chromium nitride, the excessive decrease in the etching rate caused by the chromium oxide can be suppressed, so that the cross-sectional shape of the light-shielding film pattern can be close to vertical .

(m)又，根據本實施形態，將第1反射抑制層13及第2反射抑制層15藉由使用含有Cr之濺鍍靶與包含氧系氣體、氮系氣體及稀有氣體之濺鍍氣體之反應性濺鍍進行成膜，將遮光層14藉由使用含有Cr之濺鍍靶與包含氮系氣體及稀有氣體之濺鍍氣體之反應性濺鍍進行成膜。而且，作為該等之反應性濺鍍之成膜條件，濺鍍氣體中所包含之反應性氣體之流量係選擇成為金屬模式之流量。藉此，容易將構成遮光膜12之第1反射抑制層13、遮光層14、第2反射抑制層15之各層調整為上述組成範圍，又，可有效地降低遮光膜12之正背面之反射率，且可使將遮光膜12圖案化後之遮光膜圖案之剖面形狀接近垂直。(m) According to this embodiment, the first reflection suppression layer 13 and the second reflection suppression layer 15 are combined by using a sputtering target containing Cr and a sputtering gas containing oxygen-based gas, nitrogen-based gas, and rare gas Reactive sputtering is used to form a film, and the light shielding layer 14 is formed by reactive sputtering using a sputtering target containing Cr and a sputtering gas containing a nitrogen-based gas and a rare gas. Moreover, as the film forming conditions for these reactive sputtering, the flow rate of the reactive gas contained in the sputtering gas is selected to be the flow rate of the metal mode. Thereby, it is easy to adjust each layer of the first reflection suppression layer 13, the light blocking layer 14, and the second reflection suppression layer 15 constituting the light shielding film 12 to the above composition range, and the reflectance of the front and back surfaces of the light shielding film 12 can be effectively reduced , And the cross-sectional shape of the light-shielding film pattern after patterning the light-shielding film 12 can be close to vertical.

(n)於將第1反射抑制層13及第2反射抑制層15之各層藉由反應性濺鍍而成膜時，較佳為使用氧(O2 氣體)作為氧系氣體。根據O2 氣體，由於與其他氧系氣體相比氧化力較高，故而即便於選擇金屬模式成膜之情形時，亦可將各層更確實地調整為上述組成範圍。藉此，可有效地降低遮光膜12之正背面之反射率，且可使將遮光膜12圖案化後之遮光膜圖案之剖面形狀接近垂直。(n) When forming the respective layers of the first reflection suppression layer 13 and the second reflection suppression layer 15 by reactive sputtering, it is preferable to use oxygen (O 2 gas) as the oxygen-based gas. According to the O 2 gas, since the oxidizing power is higher than other oxygen-based gases, even when the metal mode is selected for film formation, each layer can be more reliably adjusted to the above-mentioned composition range. Thereby, the reflectivity of the front and back surfaces of the light-shielding film 12 can be effectively reduced, and the cross-sectional shape of the light-shielding film pattern after the light-shielding film 12 is patterned can be made close to vertical.

(o)根據本實施形態之光罩基底1，由於正面側之反射率較低，故而於在遮光膜12上設置抗蝕劑膜，藉由描畫、顯影步驟而形成抗蝕劑圖案時，可降低描畫光之遮光膜12正面之反射。藉此，可提高抗蝕劑圖案之尺寸精度，並提高其後形成之光罩之遮光膜圖案之尺寸精度。(o) According to the photomask substrate 1 of this embodiment, since the reflectance on the front side is low, when a resist film is provided on the light-shielding film 12 and the resist pattern is formed through the drawing and development steps, it can be Reduce the reflection of the front surface of the shading film 12 of the drawing light. Thereby, the dimensional accuracy of the resist pattern can be improved, and the dimensional accuracy of the light-shielding film pattern of the mask formed later can be improved.

(p)由本實施形態之光罩基底1製造之光罩由於遮光膜圖案為高精度，且遮光膜圖案之正背面之反射率降低，故而於向被轉印體之圖案轉印時，可獲得較高之轉印特性。(p) The photomask made from the photomask substrate 1 of this embodiment has a high-precision light-shielding film pattern, and the reflectivity of the front and back of the light-shielding film pattern is reduced. Therefore, it can be obtained when the pattern is transferred to the object to be transferred. Higher transfer characteristics.

(q)又，於本實施形態中，即便於使用矩形狀且短邊之長度為850 mm以上且1620 mm以下之基板作為透明基板11，使光罩基底1大型化之情形時，亦以使膜厚方向之蝕刻速率一致之方式構成遮光膜12，故而可將對遮光膜12進行蝕刻所獲得之遮罩圖案之CD均勻性維持得較高。(q) Also, in this embodiment, even when a rectangular substrate with a short side length of 850 mm or more and 1620 mm or less is used as the transparent substrate 11, the mask base 1 is enlarged. The light-shielding film 12 is formed in a way that the etching rate in the film thickness direction is uniform, so the CD uniformity of the mask pattern obtained by etching the light-shielding film 12 can be maintained high.

(r)又，本實施形態之光罩由於可使遮光膜圖案之正背面之相對於自波長300 nm～550 nm之波長區域選擇之光的反射率均為10%以下，較佳為7.5%以下，進而較佳為5%以下，故而，例如即便於以使包含i射線、h射線及g射線之複合光曝光之方式使曝光光強度變高之情形時，亦可對於被轉印體形成較高之精度之轉印圖案。進而，於被轉印體(例如，顯示面板)之重疊附近，可防止由於照射假定以上之曝光光而產生之顯示不均。再者，作為曝光光，有包含自300 nm～550 nm之波長區域選擇之複數個波長之光之複合光，或自300 nm～550 nm之波長區域將某波長區域利用濾波器等切割而選擇之單色光，例如，有包含波長313 nm之j射線、波長365 nm之i射線、波長405 nm之h射線、及波長436 nm之g射線之複合光，或i射線之單色光等。(r) In addition, the photomask of this embodiment can make the reflectance of the front and back of the light-shielding film pattern with respect to the light selected from the wavelength range of 300 nm to 550 nm to be 10% or less, preferably 7.5% Hereinafter, it is more preferably 5% or less. Therefore, even when the exposure light intensity is increased by exposing a composite light including i-rays, h-rays, and g-rays, it can also be formed for the transferred body. Transfer patterns with higher precision. Furthermore, in the vicinity of the overlap of the transferred body (for example, a display panel), it is possible to prevent display unevenness due to exposure of the above-presumed exposure light. Furthermore, as the exposure light, there is a composite light including light of a plurality of wavelengths selected from the wavelength region of 300 nm to 550 nm, or a certain wavelength region is selected by cutting a certain wavelength region from the wavelength region of 300 nm to 550 nm using filters, etc. The monochromatic light includes, for example, composite light including j-ray with a wavelength of 313 nm, i-ray with a wavelength of 365 nm, h-ray with a wavelength of 405 nm, and g-ray with a wavelength of 436 nm, or monochromatic light of i-ray.

＜其他實施形態＞ 以上，對本發明之一實施形態具體地進行了說明，但本發明並不限定於上述實施形態，能夠於不脫離其主旨之範圍內適當變更。＜Other embodiments＞ As mentioned above, one embodiment of the present invention has been described in detail, but the present invention is not limited to the above-mentioned embodiment, and can be appropriately changed without departing from the gist of the present invention.

於上述實施形態中，對於透明基板11之上直接設置遮光膜12之情形時進行了說明，但本發明並不限定於此。例如，亦可為將光學濃度較遮光膜12低之半透光膜設置於透明基板與遮光膜12之間的光罩基底。該光罩基底可用作具有將於製造顯示裝置時所使用之光罩之片數削減之效果的灰色調遮罩或階調遮罩之光罩基底。該灰色調遮罩或階調遮罩中之遮罩圖案成為半透光膜圖案及/或遮光膜圖案。 又，亦可為代替半透光膜而將使透過光之相位偏移之相位偏移膜設置於透明基板11與遮光膜12之間的光罩基底。該光罩基底可用作具有由相位偏移效果所帶來之較高之圖案解像性之效果的相位偏移遮罩。該相位偏移遮罩中之遮罩圖案成為相位偏移膜圖案、或相位偏移膜圖案及遮光膜圖案。 上述半透光膜及相位偏移膜係採用對於作為構成遮光膜12之材料之鉻系材料具有蝕刻選擇性之材料。作為此種材料，可使用含有鉬(Mo)、鋯(Zr)、鈦(Ti)、鉭(Ta)與矽(Si)之金屬矽化物系材料，進而採用包含氧、氮、碳、或氟之至少任一者之材料。例如，採用MoSi、ZrSi、TiSi、TaSi等金屬矽化物、金屬矽化物之氧化物、金屬矽化物之氮化物、金屬矽化物之氮氧化物、金屬矽化物之碳氮化物、金屬矽化物之碳氧化物、金屬矽化物之碳化氧化氮化物。再者，該等之半透光膜或相位偏移膜亦可為由作為功能膜而列舉之上述膜而構成之積層膜。 上述半透光膜及相位偏移膜相對於曝光光之曝光波長之透過率可於1～80%之範圍內適當調整。於本發明之遮光膜之組合中，上述半透光膜及相位偏移膜之相對於曝光光之曝光波長之透過率較佳為20～80%。藉由選擇相對於曝光光之曝光波長之透過率為20～80%之半透光膜及相位偏移膜，將本發明之遮光膜組合，可使形成有半透光膜與遮光膜之積層膜、或形成有相位偏移膜與遮光膜之積層膜中之背面之相對於曝光波長之反射率為40%以下，進而較佳為30%以下。In the above-mentioned embodiment, the case where the light-shielding film 12 is directly provided on the transparent substrate 11 has been described, but the present invention is not limited to this. For example, it may also be a mask base in which a semi-transmissive film with a lower optical density than the light-shielding film 12 is disposed between the transparent substrate and the light-shielding film 12. The mask substrate can be used as a mask substrate for a gray tone mask or a gradation mask with the effect of reducing the number of masks used in manufacturing a display device. The gray-tone mask or the mask pattern in the gradation mask becomes a semi-transparent film pattern and/or a light-shielding film pattern. In addition, instead of the semi-transmissive film, a phase shift film that shifts the phase of transmitted light may be provided on the mask base between the transparent substrate 11 and the light shielding film 12. The photomask substrate can be used as a phase shift mask with a higher pattern resolution effect brought by the phase shift effect. The mask pattern in the phase shift mask becomes a phase shift film pattern, or a phase shift film pattern and a light-shielding film pattern. The above-mentioned semi-transmissive film and phase shift film adopt materials having etching selectivity to the chromium-based material constituting the light-shielding film 12. As such materials, metal silicide-based materials containing molybdenum (Mo), zirconium (Zr), titanium (Ti), tantalum (Ta), and silicon (Si) can be used, and then used containing oxygen, nitrogen, carbon, or fluorine At least any one of the materials. For example, using MoSi, ZrSi, TiSi, TaSi and other metal silicides, oxides of metal silicides, nitrides of metal silicides, oxynitrides of metal silicides, carbon nitrides of metal silicides, and carbon of metal silicides Oxide, metal silicide carbide oxide nitride. Furthermore, these semi-transmissive films or phase shift films may also be laminated films composed of the above-mentioned films exemplified as functional films. The transmittance of the semi-transparent film and the phase shift film with respect to the exposure wavelength of the exposure light can be appropriately adjusted within the range of 1 to 80%. In the combination of the light-shielding film of the present invention, the transmittance of the semi-transparent film and the phase shift film with respect to the exposure wavelength of the exposure light is preferably 20 to 80%. By selecting a semi-transmissive film and a phase shift film with a transmittance of 20 to 80% relative to the exposure wavelength of the exposure light, the light-shielding film of the present invention can be combined to form a laminated layer of the semi-light film and the light-shielding film The reflectance with respect to the exposure wavelength of the back surface of the film or the laminated film in which the phase shift film and the light-shielding film are formed is 40% or less, and more preferably 30% or less.

又，於上述實施形態中，對第1反射抑制層13及第2反射抑制層15均為各1層之情形時進行了說明，但本發明並不限定於此。例如，亦可使各層為2層以上之複數層。In addition, in the above-mentioned embodiment, the case where the first reflection suppression layer 13 and the second reflection suppression layer 15 are each one layer has been described, but the present invention is not limited to this. For example, each layer may be a plural number of two or more layers.

又，於上述實施形態中，亦可於遮光膜12上形成由與遮光膜12具有蝕刻選擇性之材料而構成之蝕刻遮罩膜。In addition, in the above-mentioned embodiment, an etching mask film made of a material having an etching selectivity with the light-shielding film 12 may also be formed on the light-shielding film 12.

又，於上述實施形態中，亦可於透明基板11與遮光膜12之間，形成由與遮光膜具有蝕刻選擇性之材料而構成之蝕刻終止膜。上述蝕刻遮罩膜、蝕刻終止膜係由相對於作為構成遮光膜12之材料之鉻系材料具有蝕刻選擇性之材料而構成。作為此種材料，可列舉含有鉬(Mo)、鋯(Zr)、鈦(Ti)、鉭(Ta)與矽(Si)之金屬矽化物系材料、或Si、SiO、SiO2 、SiON、Si3 N4 等矽系材料。 [實施例]In addition, in the above-mentioned embodiment, an etching stop film made of a material having etching selectivity with the light-shielding film may also be formed between the transparent substrate 11 and the light-shielding film 12. The above-mentioned etching mask film and the etching stop film are composed of a material having an etching selectivity with respect to a chromium-based material constituting the light-shielding film 12. Examples of such materials include metal silicide-based materials containing molybdenum (Mo), zirconium (Zr), titanium (Ti), tantalum (Ta), and silicon (Si), or Si, SiO, SiO 2 , SiON, and Si 3 N 4 and other silicon-based materials. [Example]

其次，基於實施例對本發明更詳細地進行說明，但本發明並不限定於該等之實施例。Next, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

＜實施例1＞ (光罩基底之製作) 於本實施例中，使用線內型濺鍍裝置，根據上述實施形態所示之順序，製造如圖1所示之於基板尺寸為1220 mm×1400 mm之透明基板上使第1反射抑制層、遮光層及第2反射抑制層積層而具備遮光膜之光罩基底。<Example 1> (Making of mask substrate) In this embodiment, an in-line sputtering device was used to fabricate the first reflection suppression layer, The light-shielding layer and the second reflection suppression layer are laminated to form a mask base with a light-shielding film.

第1反射抑制層之成膜條件係將濺鍍靶設為Cr濺鍍靶，反應性氣體之流量係以成為金屬模式之方式使氧(O2 )氣體之流量自5～45 sccm之範圍選擇，使氮(N2 )氣體之流量自30～60 sccm之範圍選擇，使氬(Ar)氣體之流量自60～150 sccm之範圍選擇，並且將靶施加電力設定為2.0～6.0 kW，將靶之施加電壓設定為420～430 V之範圍。再者，第1反射抑制層之成膜時之基板搬送速度設為350 mm/min。The film forming condition of the first reflection suppression layer is to set the sputtering target as the Cr sputtering target, and the flow rate of the reactive gas is to become the metal mode so that the flow rate of the oxygen (O 2 ) gas is selected from the range of 5 to 45 sccm , The flow rate of nitrogen (N 2 ) gas is selected from the range of 30-60 sccm, the flow rate of argon (Ar) gas is selected from the range of 60-150 sccm, and the target applied power is set to 2.0-6.0 kW, and the target The applied voltage is set to the range of 420～430 V. Furthermore, the substrate transport speed during the film formation of the first reflection suppression layer was set to 350 mm/min.

遮光層之成膜條件係將濺鍍靶設為Cr濺鍍靶，反應性氣體之流量係以成為金屬模式之方式使氮(N2 )氣體之流量自1～60 sccm之範圍選擇，使氬(Ar)氣體之流量自60～200 sccm之範圍選擇，並且將靶施加電力設定為3.0～7.0 kW，將施加電壓設定為370～380 V之範圍。再者，遮光層之成膜時之基板搬送速度設為200 mm/min。The film-forming conditions of the light-shielding layer are set as the sputtering target as the Cr sputtering target, and the flow rate of the reactive gas is changed to the metal mode so that the flow rate of the nitrogen (N 2 ) gas is selected from the range of 1 to 60 sccm, so that the argon The flow rate of (Ar) gas is selected from the range of 60 to 200 sccm, and the target applied power is set to 3.0 to 7.0 kW, and the applied voltage is set to the range of 370 to 380 V. Furthermore, the substrate conveying speed during the film formation of the light-shielding layer was set to 200 mm/min.

第2反射抑制層之成膜條件係將濺鍍靶設為Cr濺鍍靶，反應性氣體之流量係以成為金屬模式之方式使氧(O2 )氣體之流量自8～45 sccm之範圍選擇，使氮(N2 )氣體之流量自30～60 sccm之範圍選擇，使氬(Ar)氣體之流量自60～150 sccm之範圍選擇，並且將靶施加電力設定為2.0～6.0 kW，將靶施加電壓設定為420～430 V之範圍。再者，第2反射抑制層之成膜時之基板搬送速度設為300 mm/min。The film forming condition of the second reflection suppression layer is to set the sputtering target as the Cr sputtering target, and the flow rate of the reactive gas is to become the metal mode so that the flow rate of the oxygen (O 2 ) gas is selected from the range of 8 to 45 sccm , The flow rate of nitrogen (N 2 ) gas is selected from the range of 30-60 sccm, the flow rate of argon (Ar) gas is selected from the range of 60-150 sccm, and the target applied power is set to 2.0-6.0 kW, and the target The applied voltage is set in the range of 420 to 430 V. Furthermore, the substrate transport speed during the film formation of the second reflection suppression layer was set to 300 mm/min.

關於所獲得之光罩基底之遮光膜，藉由X射線光電子分光法(XPS)而測定膜厚方向之組成，結果確認到遮光膜中之各層具有圖2所示之組成分佈。圖2係表示實施例1之光罩基底中之膜厚方向之組成分析結果的圖，橫軸表示濺鍍時間，縱軸表示元素之含有率[原子%]。濺鍍時間表示距遮光膜之表面之深度。Regarding the obtained light-shielding film of the mask base, the composition in the film thickness direction was measured by X-ray photoelectron spectroscopy (XPS). As a result, it was confirmed that each layer in the light-shielding film had the composition distribution shown in FIG. 2. 2 is a graph showing the result of composition analysis in the film thickness direction of the mask substrate of Example 1. The horizontal axis represents the sputtering time, and the vertical axis represents the element content [atom %]. The sputtering time indicates the depth from the surface of the shading film.

於圖2中，自表面至深度約5 min(分鐘)為止之區域係表面自然氧化層，自深度約5 min(分鐘)至深度約16 min(分鐘)為止之區域係第2反射抑制層，自深度約16 min(分鐘)至深度約40 min(分鐘)為止之區域係過渡層，自深度約40 min(分鐘)至深度約97 min(分鐘)為止之區域係遮光層，自深度約97 min(分鐘)至深度約124 min(分鐘)為止之區域係過渡層，自深度約124 min(分鐘)至深度約132 min(分鐘)為止之區域係第1反射抑制層，距深度約132 min(分鐘)之區域係透明基板。 再者，藉由膜厚計而測定出之遮光膜之膜厚係198 nm，上述表面自然氧化層、第2反射抑制層、過渡層、遮光層、過渡層、第1反射抑制層之各膜厚係表面自然氧化層為約4 nm，第2反射抑制層為約21 nm，過渡層為約35 nm，遮光層為約88 nm，過渡層為約39 nm，第1反射抑制層為約11 nm。In Figure 2, the area from the surface to the depth of about 5 min (minutes) is the surface natural oxide layer, and the area from the depth of about 5 min (minutes) to the depth of about 16 min (minutes) is the second reflection suppression layer. The region from a depth of about 16 min (minutes) to a depth of about 40 min (minutes) is a transition layer, and the region from a depth of about 40 min (minutes) to a depth of about 97 min (minutes) is a light-shielding layer, from a depth of about 97 The area from min (minute) to the depth of about 124 min (minute) is the transition layer, and the area from the depth of about 124 min (minute) to the depth of about 132 min (minute) is the first reflection suppression layer, and the distance from the depth is about 132 min. The area in (minutes) is a transparent substrate. Furthermore, the film thickness of the light-shielding film measured by a film thickness meter is 198 nm, and the above-mentioned surface natural oxide layer, the second reflection suppression layer, the transition layer, the light-shielding layer, the transition layer, and the first reflection suppression layer are each film The thickness of the natural oxide layer on the thick surface is about 4 nm, the second reflection suppression layer is about 21 nm, the transition layer is about 35 nm, the light shielding layer is about 88 nm, the transition layer is about 39 nm, and the first reflection suppression layer is about 11 nm.

如圖2所示，第1反射抑制層係CrON膜，包含55.4原子%之Cr、20.8原子%之N、23.8原子%之O。該等元素之含有率係於第1反射抑制層中之N成為峰值之部分(濺鍍時間為123 min(分鐘)之區域)測定出者。第1反射抑制層具有如圖2所示之傾斜組成，且具有朝向膜厚方向之透明基板而O含有率增加並且N含有率降低之部分。再者，於第1反射抑制層中，各元素之膜厚方向上之平均含有率係Cr為57原子%，N為18原子%，O為25原子%。As shown in FIG. 2, the first reflection suppression layer is a CrON film, which contains 55.4 atomic% of Cr, 20.8 atomic% of N, and 23.8 atomic% of O. The content of these elements is measured in the part where N in the first reflection suppression layer becomes the peak (the area where the sputtering time is 123 min (minutes)). The first reflection suppression layer has an inclined composition as shown in FIG. 2 and has a transparent substrate facing the film thickness direction, where the O content increases and the N content decreases. Furthermore, in the first reflection suppression layer, the average content of each element in the film thickness direction is 57 atomic% for Cr, 18 atomic% for N, and 25 atomic% for O.

遮光層係CrN膜，包含92.0原子%之Cr、8.0原子%之N。該等元素之含有率係於遮光層之膜厚方向中之中心部分(濺鍍時間為69 min(分鐘)之區域)測定出者。再者，於遮光層中，各元素之膜厚方向上之平均含有率係Cr為91原子%，N為9原子%。The light-shielding layer is a CrN film, which contains 92.0 atomic% of Cr and 8.0 atomic% of N. The content of these elements is measured in the central part (the area where the sputtering time is 69 min (minutes)) in the film thickness direction of the light-shielding layer. Furthermore, in the light-shielding layer, the average content of each element in the film thickness direction is 91 atomic% for Cr and 9 atomic% for N.

第2反射抑制層係CrON膜，包含50.7原子%之Cr、12.2原子%之N、37.1原子%之O。該等元素之含有率係於第2反射抑制層中之O增加之區域之中心部分(濺鍍時間為16 min(分鐘)之區域)測定出者。第2反射抑制層具有如圖2所示之傾斜組成，且具有朝向膜厚方向之遮光層側而O含有率增加並且N含有率降低之部分。再者，於第2反射抑制層中，各元素之膜厚方向上之平均含有率係Cr為52原子%，N為17原子%，O為31原子%。又，認為，於第2反射抑制層之表面，藉由曝露於大氣而形成表面自然氧化層，由於該層氧化或者碳化，故而檢測出較高的O含有率及C含有率。The second reflection suppression layer is a CrON film, which contains 50.7 atomic% of Cr, 12.2 atomic% of N, and 37.1 atomic% of O. The content of these elements is measured in the central part of the area where O increases in the second reflection suppression layer (the area where the sputtering time is 16 min (minutes)). The second reflection suppression layer has a sloped composition as shown in FIG. 2 and has a portion where the O content increases and the N content decreases toward the light-shielding layer side in the film thickness direction. Furthermore, in the second reflection suppression layer, the average content of each element in the film thickness direction is 52 atomic% for Cr, 17 atomic% for N, and 31 atomic% for O. In addition, it is considered that a natural oxidation layer on the surface is formed by exposure to the atmosphere on the surface of the second reflection suppression layer, and because this layer is oxidized or carbonized, high O content and C content are detected.

又，基於XPS測定結果而對構成遮光膜之第1反射抑制層、遮光層、第2反射抑制層之各層之鍵結狀態(化學狀態)進行光譜解析。其結果，第1反射抑制層與第2反射抑制層係包含氮化鉻(CrN)、氧化鉻(III)(Cr2 O3 )及氧化鉻(VI)(CrO3 )且含有鉻、氧及氮之鉻系材料(鉻化合物)。又，遮光層係包含鉻(Cr)與氮化二鉻(Cr2 N)且含有鉻與氮之鉻系材料(鉻化合物)。Furthermore, based on the XPS measurement result, the bonding state (chemical state) of each layer of the first reflection suppressing layer, the light shielding layer, and the second reflection suppressing layer constituting the light shielding film was analyzed by spectrum. As a result, the first reflection suppression layer and the second reflection suppression layer contain chromium nitride (CrN), chromium oxide (III) (Cr 2 O 3 ), and chromium oxide (VI) (CrO 3 ), and contain chromium, oxygen, and Nitrogen-based chromium materials (chromium compounds). In addition, the light-shielding layer is a chromium-based material (chromium compound) containing chromium (Cr) and chromium nitride (Cr 2 N), and containing chromium and nitrogen.

(光罩基底之評估) 關於實施例1之光罩基底，藉由以下所示之方法而對遮光膜之光學濃度、遮光膜之正背面之反射率進行評估。(Evaluation of mask substrate) Regarding the mask substrate of Example 1, the optical density of the light-shielding film and the reflectivity of the front and back surfaces of the light-shielding film were evaluated by the method shown below.

關於實施例1之光罩基底，藉由分光光度計(島津製作所股份有限公司製造「SolidSpec-3700」)而對遮光膜之光學濃度進行測定，結果，於作為曝光光之波長區域之g射線(波長436 nm)中為5.0。又，藉由分光光度計(股份有限公司島津製作所製造「SolidSpec-3700」)而對遮光膜之正背面之反射率進行測定。具體而言，藉由分光光度計而分別對遮光膜之第2反射抑制層側之反射率(正面反射率)、與遮光膜之透明基板側之反射率(背面反射率)進行測定。其結果，獲得如圖3所示之反射率光譜。圖3係表示關於實施例1之光罩基底之正背面之反射率光譜，橫軸表示波長[nm]，縱軸表示反射率[%]。如圖3所示，實施例1之光罩基底中，確認到可使正背面之反射率光譜之底部峰值波長為436 nm附近，又可相對於廣泛之波長之光使反射率大幅度降低。具體而言，於波長365 nm～436 nm中，遮光膜之正面反射率為10.0%以下(7.7%(波長365 nm)、1.8%(波長405 nm)、1.1%(波長413 nm)、0.3%(波長436 nm))，遮光膜之背面反射率為7.5%以下(6.2%(波長365 nm)、4.7%(波長405 nm)、4.8%(波長436 nm))。確認到於波長365 nm～436 nm中可使遮光膜之正背面之反射率降低至10%以下，尤其關於相對於波長436 nm之光之反射率，可使正面反射率為0.3%，使背面反射率為4.8%。Regarding the mask substrate of Example 1, the optical density of the light-shielding film was measured by a spectrophotometer ("SolidSpec-3700" manufactured by Shimadzu Corporation). As a result, the g-ray ( The wavelength is 436 nm) 5.0. In addition, the reflectance of the front and back of the light-shielding film was measured with a spectrophotometer ("SolidSpec-3700" manufactured by Shimadzu Corporation). Specifically, the reflectance on the second reflection suppression layer side of the light-shielding film (front reflectance) and the reflectance on the transparent substrate side of the light-shielding film (back reflectance) were measured with a spectrophotometer. As a result, the reflectance spectrum shown in Fig. 3 was obtained. Fig. 3 shows the reflectance spectrum of the front and back of the photomask substrate of Example 1. The horizontal axis represents the wavelength [nm], and the vertical axis represents the reflectance [%]. As shown in Fig. 3, in the photomask substrate of Example 1, it was confirmed that the bottom peak wavelength of the reflectance spectrum of the front and back sides can be around 436 nm, and the reflectance can be greatly reduced compared to light of a wide range of wavelengths. Specifically, in the wavelength of 365 nm ~ 436 nm, the front reflectance of the shading film is 10.0% or less (7.7% (wavelength 365 nm), 1.8% (wavelength 405 nm), 1.1% (wavelength 413 nm), 0.3% (Wavelength 436 nm)), the back surface reflectance of the shading film is below 7.5% (6.2% (wavelength 365 nm), 4.7% (wavelength 405 nm), 4.8% (wavelength 436 nm)). It has been confirmed that the reflectance of the front and back of the light shielding film can be reduced to less than 10% at a wavelength of 365 nm to 436 nm, especially with regard to the reflectance of light with a wavelength of 436 nm, the front reflectance can be 0.3%, and the back The reflectivity is 4.8%.

(遮光膜圖案之評估) 使用實施例1之光罩基底，於透明基板上形成遮光膜圖案。具體而言，於透明基板上之遮光膜上形成酚醛系之正型抗蝕劑膜之後，進行雷射描畫(波長413 nm)、顯影處理而形成抗蝕劑圖案。然後，使抗蝕劑圖案為遮罩並藉由鉻蝕刻液而進行濕式蝕刻，於透明基板上形成遮光膜圖案。遮光膜圖案之評估係藉由形成1.9 μm之線與間隙圖案並利用掃描電子顯微鏡(SEM)觀察遮光膜圖案之剖面形狀而進行。其結果，如圖4所示，確認到使剖面形狀接近垂直。圖4係用以說明關於實施例1之光罩基底，由濕式蝕刻而實現之遮光膜圖案之剖面形狀之垂直性之圖，且分別表示以恰蝕刻時間(JET)為基準(100%)，使蝕刻時間為110%、130%、150%而進行過蝕刻後之剖面形狀。於圖4中，確認到於透明基板上積層有遮光膜圖案及抗蝕劑膜圖案，遮光膜圖案之側面係於JET 100%時，與透明基板所成之角為70°。確認到該所成之角即便於使蝕刻時間為JET之110%、130%及150%時，亦係60°～80°之範圍內，無論蝕刻時間如何，均可使遮光膜圖案之剖面形狀穩定地形成為垂直。(Evaluation of shading film pattern) Using the mask base of Example 1, a light-shielding film pattern is formed on the transparent substrate. Specifically, after forming a phenolic-based positive resist film on the light-shielding film on the transparent substrate, laser drawing (wavelength 413 nm) and development are performed to form a resist pattern. Then, the resist pattern is used as a mask and wet etching is performed with a chromium etching solution to form a light-shielding film pattern on the transparent substrate. The evaluation of the light-shielding film pattern was performed by forming a 1.9 μm line and gap pattern and observing the cross-sectional shape of the light-shielding film pattern with a scanning electron microscope (SEM). As a result, as shown in FIG. 4, it was confirmed that the cross-sectional shape was made close to vertical. 4 is a diagram for explaining the verticality of the cross-sectional shape of the light-shielding film pattern realized by wet etching with respect to the photomask substrate of Example 1, and respectively shows that it is based on the just etching time (JET) (100%) , Make the etching time 110%, 130%, 150% and the cross-sectional shape after etching. In FIG. 4, it is confirmed that a light-shielding film pattern and a resist film pattern are laminated on the transparent substrate. When the side of the light-shielding film pattern is JET 100%, the angle formed with the transparent substrate is 70°. It is confirmed that the angle formed is within the range of 60°～80° even when the etching time is 110%, 130%, and 150% of JET. Regardless of the etching time, the cross-sectional shape of the light-shielding film pattern can be made The stable terrain becomes vertical.

如以上之實施例1般，關於光罩基底之遮光膜，自透明基板側使第1反射抑制層、遮光層及第2反射抑制層積層，以使各層成為特定之組成之方式構成，藉此，可使正背面之反射率於廣泛之波長範圍降低，並且可將藉由濕式蝕刻而圖案化後之遮光膜圖案之剖面形狀形成為垂直。As in Example 1 above, regarding the light-shielding film of the mask base, the first reflection-inhibiting layer, the light-shielding layer, and the second reflection-inhibiting layer are laminated from the transparent substrate side so that each layer has a specific composition. , The reflectance of the front and back sides can be reduced in a wide range of wavelengths, and the cross-sectional shape of the light-shielding film pattern patterned by wet etching can be formed to be vertical.

(光罩之製作) 其次，使用實施例1之光罩基底，製作光罩。 首先，於光罩基底之遮光膜上形成酚醛系之正型抗蝕劑。然後，使用雷射描畫裝置，對該抗蝕劑膜描畫TFT面板用之電路圖案之圖案，進而藉由顯影、沖洗，而形成特定之抗蝕劑圖案(上述電路圖案之最小線寬為0.75 μm)。 然後，使抗蝕劑圖案為遮罩，使用鉻蝕刻液，利用濕式蝕刻使遮光膜圖案化，最後藉由抗蝕劑剝離液而將抗蝕劑圖案剝離，獲得於透明基板上形成有遮光膜圖案(遮罩圖案)之光罩。 藉由精工電子奈米科技股份有限公司製造「SIR8000」而測定該光罩之遮光膜圖案之CD均勻性。CD均勻性之測定係關於將基板之周緣區域除外之1100 mm×1300 mm之區域，於11×11之位置進行測定。 其結果，CD均勻性為100 nm，所獲得之光罩之CD均勻性良好。(Making of Mask) Next, the mask substrate of Example 1 was used to fabricate a mask. First, a phenolic-based positive resist is formed on the light-shielding film of the mask substrate. Then, use a laser drawing device to draw the pattern of the circuit pattern for the TFT panel on the resist film, and then develop and rinse to form a specific resist pattern (the minimum line width of the above circuit pattern is 0.75 μm ). Then, the resist pattern is used as a mask, and a chromium etching solution is used to pattern the light-shielding film by wet etching. Finally, the resist pattern is peeled off by the resist stripping liquid to obtain a light-shielding formed on the transparent substrate. The mask of the film pattern (mask pattern). The CD uniformity of the light-shielding film pattern of the mask was measured by "SIR8000" manufactured by Seiko Nano Technology Co., Ltd. The measurement of CD uniformity is about the area of 1100 mm×1300 mm excluding the peripheral area of the substrate, and the measurement is carried out at the position of 11×11. As a result, the CD uniformity was 100 nm, and the CD uniformity of the obtained photomask was good.

(LCD面板之製作) 將於該實施例1中製作出之光罩設置於曝光裝置之遮罩載台，對在顯示裝置(TFT)用之基板上形成有抗蝕劑膜之被轉印體進行圖案曝光而製作TFT陣列。作為曝光光，使用包含波長365 nm之i射線、波長405 nm之h射線、及波長436 nm之g射線之波長300 nm以上且550 nm以下之複合光。 將所製作出之TFT陣列與彩色濾光片、偏光板、背光組合而製作TFT-LCD面板。其結果，獲得無顯示不均之TFT-LCD面板。(Production of LCD panel) The mask produced in Example 1 was set on the mask stage of the exposure device, and the transferred body on which the resist film was formed on the substrate for the display device (TFT) was subjected to pattern exposure to produce TFT Array. As the exposure light, composite light with a wavelength of 300 nm or more and 550 nm or less including i-ray with a wavelength of 365 nm, h-ray with a wavelength of 405 nm, and g-ray with a wavelength of 436 nm is used. Combine the produced TFT array with color filters, polarizers, and backlight to produce a TFT-LCD panel. As a result, a TFT-LCD panel with no display unevenness was obtained.

＜實施例2＞ (光罩基底之製作) 於本實施例中，除了於透明基板與遮光膜之間形成半透光膜以外，與實施例1相同地製造光罩基底。具體而言，於在1220 mm×1400 mm之透明基板上形成半透光膜之後，以與實施例1相同之條件使第1反射抑制層、遮光層及第2反射抑制層積層，藉此製造實施例2之光罩基底。 半透光膜之成膜係將濺鍍靶設為MoSi濺鍍靶，藉由利用氬(Ar)氣體與氮(N2 )氣體之混合氣體之反應性濺鍍，而形成鉬矽化物氮化膜(MoSiN)。該半透光膜係於i射線(波長365 nm)中，以透過率成為40%之方式，適當調整組成比與膜厚。 其次，與實施例1相同地，於上述半透光膜上形成由第1反射抑制層、遮光層及第2反射抑制層構成之遮光膜而製造實施例2之光罩基底。<Example 2> (Production of a photomask base) In this example, a photomask base was manufactured in the same manner as in Example 1, except that a semi-transparent film was formed between the transparent substrate and the light-shielding film. Specifically, after forming a translucent film on a transparent substrate of 1220 mm×1400 mm, the first reflection suppression layer, the light shielding layer, and the second reflection suppression layer were laminated under the same conditions as in Example 1, thereby manufacturing The mask substrate of Example 2. The semi-transparent film is formed by using the sputtering target as the MoSi sputtering target, and the molybdenum silicide nitriding is formed by reactive sputtering using a mixed gas of argon (Ar) gas and nitrogen (N 2) gas Film (MoSiN). The semi-transmissive film is in i-ray (wavelength 365 nm), and the composition ratio and film thickness are appropriately adjusted so that the transmittance becomes 40%. Next, in the same manner as in Example 1, a light shielding film composed of a first reflection suppressing layer, a light shielding layer, and a second reflection suppressing layer was formed on the above-mentioned semi-transparent film to manufacture a mask base of Example 2.

(光罩基底之評估) 關於實施例2之光罩基底，藉由與上述實施例1相同之方法而評估由半透光膜與遮光膜而構成之積層膜之光學濃度與正背面之反射率。其結果，作為曝光光之波長區域之g射線(波長436 nm)中之積層膜之光學濃度為5.0以上。又，於波長365 nm～436 nm中，積層膜之遮光膜側之反射率(正面反射率)為10.0%以下(7.7%(波長365 nm)、1.8%(波長405 nm)、1.1%(波長413 nm)、0.3%(波長436 nm))，半透光膜側之反射率(背面反射率)為30.0%以下(27.4%(波長365 nm)、22.5%(波長405 nm)、20.1%(波長436 nm))。(Evaluation of mask substrate) Regarding the photomask substrate of Example 2, the optical density of the laminated film composed of the semi-transmissive film and the light-shielding film and the reflectance of the front and back surfaces were evaluated by the same method as the above-mentioned Example 1. As a result, the optical density of the laminated film in the g-ray (wavelength 436 nm) which is the wavelength region of the exposure light is 5.0 or more. In addition, in the wavelength of 365 nm to 436 nm, the reflectance (frontal reflectance) of the light-shielding film side of the laminated film is 10.0% or less (7.7% (wavelength 365 nm), 1.8% (wavelength 405 nm), 1.1% (wavelength 413 nm), 0.3% (wavelength 436 nm)), the reflectance of the semi-transmissive film side (back surface reflectance) is 30.0% or less (27.4% (wavelength 365 nm), 22.5% (wavelength 405 nm), 20.1% ( Wavelength 436 nm)).

(光罩之製作) 其次，使用實施例2之光罩基底，製作光罩。該光罩係於透明基板上形成有半透光膜圖案，於該半透光膜圖案上形成有遮光膜圖案，且具備包含透光部、遮光部、半透光部之轉印圖案。實施例2之光罩係藉由專利第4934236號中所記載之灰色調遮罩之製造方法而製造。該所獲得之光罩之半透光膜圖案及遮光膜圖案之CD均勻性良好。(Making of Mask) Next, the mask substrate of Example 2 was used to fabricate a mask. The photomask is formed with a semi-transmissive film pattern on a transparent substrate, a light-shielding film pattern is formed on the semi-transparent film pattern, and is provided with a transfer pattern including a light-transmitting part, a light-shielding part, and a semi-light-transmitting part. The mask of Example 2 is manufactured by the manufacturing method of the gray tone mask described in Patent No. 4934236. The CD uniformity of the semi-transmissive film pattern and the light-shielding film pattern of the obtained mask is good.

(LCD面板之製作) 使用該實施例2中製作出之光罩，與實施例1相同地製作LCD面板。其結果，獲得無顯示不均之TFT-LCD面板。再者，作為實施例2之光罩之製造方法，可藉由專利第5605917號中所記載之光罩之製造方法而製作，藉由該方法而獲得之光罩之半透光膜圖案及遮光膜圖案之CD均勻性亦良好。而且，獲得顯示不均較少之TFT-LCD面板。(Production of LCD panel) Using the photomask fabricated in Example 2, the LCD panel was fabricated in the same manner as in Example 1. As a result, a TFT-LCD panel with no display unevenness was obtained. Furthermore, as the manufacturing method of the photomask of Example 2, it can be manufactured by the manufacturing method of the photomask described in Patent No. 5605917, and the semi-transparent film pattern and light-shielding film of the photomask obtained by this method The CD uniformity of the film pattern is also good. Moreover, a TFT-LCD panel with less display unevenness is obtained.

＜比較例1＞ 作為比較例，製造於基板尺寸為1220 mm×1400 mm之透明基板上，使第1反射抑制層、遮光層及第2反射抑制層積層而具備遮光膜之光罩基底。<Comparative example 1> As a comparative example, it was fabricated on a transparent substrate with a substrate size of 1220 mm×1400 mm, and a first reflection suppression layer, a light shielding layer, and a second reflection suppression layer were laminated to form a mask base with a light shielding film.

第1反射抑制層之成膜條件係將濺鍍靶設為Cr濺鍍靶，反應性氣體之流量係以成為反應模式之方式使氧(O2 )氣體之流量自150～300 sccm之範圍選擇，使氮(N2 )氣體之流量自150～300 sccm之範圍選擇，使甲烷(CH4 )氣體之流量自5～15 sccm之範圍選擇，使氬(Ar)氣體之流量自100～150 sccm之範圍選擇，並且將靶施加電力設定為2.0～7.0 kW之範圍。再者，第1反射抑制層之成膜時之基板搬送速度設為200 mm/min，進行3次成膜。The film forming condition of the first reflection suppression layer is to set the sputtering target as the Cr sputtering target, and the flow rate of the reactive gas is to become the reaction mode so that the flow rate of the oxygen (O 2 ) gas is selected from the range of 150 to 300 sccm , The flow rate of nitrogen (N 2 ) gas is selected from the range of 150 to 300 sccm, the flow rate of methane (CH 4 ) gas is selected from the range of 5 to 15 sccm, and the flow rate of argon (Ar) gas is selected from 100 to 150 sccm Select the range, and set the target applied power to the range of 2.0 to 7.0 kW. In addition, the substrate transport speed during the film formation of the first reflection suppression layer was set to 200 mm/min, and the film formation was performed three times.

遮光層之成膜條件係將濺鍍靶設為Cr濺鍍靶，反應性氣體之流量係以成為金屬模式之方式使氮(N2 )氣體之流量自1～60 sccm之範圍選擇，使氬(Ar)氣體之流量自60～200 sccm之範圍選擇，並且將靶施加電力設定為5.0～8.0 kW之範圍。再者，遮光層之成膜時之基板搬送速度設為200 mm/min。The film-forming conditions of the light-shielding layer are set as the sputtering target as the Cr sputtering target, and the flow rate of the reactive gas is changed to the metal mode so that the flow rate of the nitrogen (N 2 ) gas is selected from the range of 1 to 60 sccm, so that the argon The flow rate of (Ar) gas is selected from the range of 60 to 200 sccm, and the target applied power is set to the range of 5.0 to 8.0 kW. Furthermore, the substrate conveying speed during the film formation of the light-shielding layer was set to 200 mm/min.

第2反射抑制層之成膜條件係將濺鍍靶設為Cr濺鍍靶，反應性氣體之流量係以成為反應模式之方式使氧(O2 )氣體之流量自150～300之範圍選擇，使氮(N2 )氣體之流量自150～300 sccm之範圍選擇，使甲烷(CH4 )氣體之流量自5～15 sccm之範圍選擇，使氬(Ar)氣體之流量自100～150 sccm之範圍選擇，並且將靶施加電力設定為2.0～7.0 kW之範圍。再者，第2反射抑制層之成膜時之基板搬送速度設為200 mm/min，進行3次成膜。 藉由膜厚計而測定出之遮光膜之膜厚為206 nm。再者，表面自然氧化層、第2反射抑制層、遮光層、第1反射抑制層之各膜厚為約3 nm，第2反射抑制層為約51 nm，遮光層為約101 nm，第1反射抑制層為約51 nm。又，於第2反射抑制層與遮光層之間、遮光層與第1反射抑制層之間，形成有各元素之組成連續地傾斜之過渡層。The film forming condition of the second reflection suppression layer is to set the sputtering target as the Cr sputtering target, and the flow rate of the reactive gas is such that the flow rate of the oxygen (O 2 ) gas is selected from the range of 150 to 300 so that the flow rate of the reactive gas becomes the reaction mode. The flow rate of nitrogen (N 2 ) gas is selected from the range of 150 to 300 sccm, the flow rate of methane (CH 4 ) gas is selected from the range of 5 to 15 sccm, and the flow rate of argon (Ar) gas is selected from 100 to 150 sccm. Select the range, and set the target applied power to the range of 2.0 to 7.0 kW. In addition, the substrate transport speed during the film formation of the second reflection suppression layer was set to 200 mm/min, and the film formation was performed three times. The thickness of the light-shielding film measured by a film thickness meter was 206 nm. Furthermore, the thickness of each of the surface natural oxide layer, the second reflection suppression layer, the light shielding layer, and the first reflection suppression layer is about 3 nm, the second reflection suppression layer is about 51 nm, and the light shielding layer is about 101 nm. The reflection suppression layer is about 51 nm. Furthermore, between the second reflection suppression layer and the light-shielding layer, and between the light-shielding layer and the first reflection suppression layer, a transition layer in which the composition of each element is continuously inclined is formed.

關於比較例1之光罩基底之遮光膜，對各層中所包含之元素之含有率進行測定，結果如以下所述。再者，以下所示之各層之含有率表示各元素之膜厚方向上之平均含有率。 第1反射抑制層係CrON膜，包含45原子%之Cr、3原子%之N、52原子%之O。 遮光層係CrN膜，包含78原子%之Cr、22原子%之N。 第2反射抑制層係CrON膜，包含45原子%之Cr、3原子%之N、52原子%之O。Regarding the light-shielding film of the mask base of Comparative Example 1, the content rate of the elements contained in each layer was measured, and the results are as follows. In addition, the content rate of each layer shown below represents the average content rate of each element in the film thickness direction. The first reflection suppression layer is a CrON film, containing 45 atomic% of Cr, 3 atomic% of N, and 52 atomic% of O. The light-shielding layer is a CrN film, containing 78 atomic% of Cr and 22 atomic% of N. The second reflection suppression layer is a CrON film, containing 45 atomic% of Cr, 3 atomic% of N, and 52 atomic% of O.

與上述實施例1相同地，關於比較例1之光罩基底，對遮光膜之光學濃度、遮光膜之正背面之反射率進行測定。其結果，遮光膜之光學濃度係於作為曝光光之波長區域之g射線(波長436 nm)中為3.5%，於i射線(波長365 nm)中為4.5%。又，於波長365 nm～436 nm中，遮光膜之正面反射率為5.0%以下(4.5%(波長365 nm)、4.0%(波長405 nm)、3.5%(波長436 nm))，遮光膜之背面反射率為7.5%以下(5.5%(波長365 nm)、6.5%(波長405 nm)、7.5%(波長436 nm))。 進而，與實施例1相同地進行遮光膜圖案之評估。其結果，遮光膜圖案之側面係於透明基板附近成為錐形狀，於抗蝕劑膜附近成為倒錐形狀，剖面形狀成為非常差之結果。再者，確認到JET 100%時之與透明基板所成之角為150°。In the same manner as in Example 1, regarding the mask substrate of Comparative Example 1, the optical density of the light-shielding film and the reflectance of the front and back surfaces of the light-shielding film were measured. As a result, the optical density of the light-shielding film is 3.5% in the g-ray (wavelength of 436 nm) as the wavelength region of the exposure light, and 4.5% in the i-ray (wavelength of 365 nm). In addition, in the wavelength of 365 nm～436 nm, the frontal reflectance of the light-shielding film is 5.0% or less (4.5% (wavelength 365 nm), 4.0% (wavelength 405 nm), 3.5% (wavelength 436 nm)). The back reflectance is 7.5% or less (5.5% (wavelength 365 nm), 6.5% (wavelength 405 nm), 7.5% (wavelength 436 nm)). Furthermore, the evaluation of the light-shielding film pattern was performed in the same manner as in Example 1. As a result, the side surface of the light-shielding film pattern becomes a tapered shape near the transparent substrate and an inverted tapered shape near the resist film, resulting in a very poor cross-sectional shape. Furthermore, it was confirmed that the angle between JET and the transparent substrate is 150° when JET is 100%.

其次，使用比較例1之光罩基底，與實施例1相同地製作光罩。對所獲得之光罩之遮光膜圖案之CD均勻性進行測定，結果較差，為200 nm。如此，於比較例1之遮罩基底中，可降低正背面之反射率，但無法形成高精度之遮罩圖案。Next, using the photomask substrate of Comparative Example 1, a photomask was produced in the same manner as in Example 1. The CD uniformity of the light-shielding film pattern of the obtained mask was measured, and the result was poor, which was 200 nm. In this way, in the mask base of Comparative Example 1, the reflectivity of the front and back surfaces can be reduced, but a high-precision mask pattern cannot be formed.

如以上般，於光罩基底之遮光膜中，第1反射抑制層、遮光層及第2反射抑制層之各者由具有特定組成之材料而形成，並且以使遮光膜之正背面各自之反射率為10%以下，且光學濃度成為3.0以上之方式設定各層之膜厚，而構成光罩基底，藉此，於藉由蝕刻而製作光罩時，可獲得CD均勻性良好且高精度之遮罩圖案。根據此種光罩，可製作顯示不均較少之顯示裝置。As above, in the light-shielding film of the mask base, each of the first reflection-inhibiting layer, the light-shielding layer, and the second reflection-inhibiting layer is formed of a material with a specific composition, and the front and back sides of the light-shielding film are reflected respectively The film thickness of each layer is set in such a way that the rate is 10% or less and the optical density becomes 3.0 or more to form the mask base. By this, when the mask is produced by etching, a CD uniformity and high-precision mask can be obtained. Hood pattern. According to this type of photomask, a display device with less display unevenness can be manufactured.

1:光罩基底 11:透明基板 12:遮光膜 13:第1反射抑制層 14:遮光層 15:第2反射抑制層1: Mask base 11: Transparent substrate 12: Shading film 13: The first reflection suppression layer 14: shading layer 15: The second reflection suppression layer

圖1係表示本發明之一實施形態之光罩基底之概略構成之剖視圖。 圖2係表示實施例1之光罩基底中之膜厚方向之組成分析結果之圖。 圖3係針對實施例1之光罩基底表示正背面之反射率光譜之圖。 圖4係用以說明使用實施例1之光罩基底製作出之光罩之遮光膜圖案之剖面形狀之特性的圖。 圖5係用以說明利用反應性濺鍍形成遮光膜之情形時之成膜模式之模式圖。Fig. 1 is a cross-sectional view showing a schematic configuration of a photomask substrate according to an embodiment of the present invention. FIG. 2 is a diagram showing the composition analysis result of the film thickness direction in the mask substrate of Example 1. FIG. FIG. 3 is a graph showing the reflectance spectrum of the front and back of the mask substrate of Example 1. FIG. 4 is a diagram for explaining the characteristics of the cross-sectional shape of the light-shielding film pattern of the photomask fabricated using the photomask substrate of Example 1. FIG. FIG. 5 is a schematic diagram for explaining the film forming mode when the light shielding film is formed by reactive sputtering.

1:光罩基底 1: Mask base

11:透明基板 11: Transparent substrate

12:遮光膜 12: Shading film

13:第1反射抑制層 13: The first reflection suppression layer

14:遮光層 14: shading layer

15:第2反射抑制層 15: The second reflection suppression layer

Claims (16)

一種光罩基底，其特徵在於：其係於製作顯示裝置製造用之光罩時使用之光罩基底，且具有： 透明基板，其由相對於曝光光實質上透明之材料而構成； 遮光膜，其設置於上述透明基板上，且由相對於上述曝光光實質上不透明之材料而構成； 上述遮光膜係自上述透明基板側起具備第1反射抑制層、遮光層及第2反射抑制層， 上述第1反射抑制層係含有鉻、氧及氮之鉻系材料，且具有鉻之含有率為25～75原子%、氧之含有率為15～45原子%、氮之含有率為10～30原子%之組成， 上述第2反射抑制層係含有鉻、氧及氮之鉻系材料，且具有鉻之含有率為30～75原子%、氧之含有率為20～50原子%、氮之含有率為5～20原子%之組成， 以使上述遮光膜之正面及背面之相對於上述曝光光之曝光波長之反射率分別為10%以下，正面側之反射率較背面側之反射率低，且光學濃度成為3.0以上之方式，設定上述第1反射抑制層、上述遮光層、及上述第2反射抑制層之膜厚。A photomask substrate, which is characterized in that it is a photomask substrate used when manufacturing a photomask for manufacturing a display device, and has: A transparent substrate, which is composed of a material that is substantially transparent to the exposure light; A light-shielding film, which is provided on the above-mentioned transparent substrate and is made of a material that is substantially opaque with respect to the above-mentioned exposure light; The light-shielding film includes a first reflection-inhibiting layer, a light-shielding layer, and a second reflection-inhibiting layer from the transparent substrate side, and The first reflection suppression layer is a chromium-based material containing chromium, oxygen and nitrogen, and has a chromium content of 25 to 75 atomic %, an oxygen content of 15 to 45 atomic %, and a nitrogen content of 10 to 30 The composition of atomic %, The second reflection suppression layer is a chromium-based material containing chromium, oxygen, and nitrogen, and has a chromium content of 30 to 75 atomic %, an oxygen content of 20 to 50 atomic %, and a nitrogen content of 5 to 20 The composition of atomic %, Set so that the reflectance of the front and back of the light-shielding film with respect to the exposure wavelength of the exposure light is 10% or less, the reflectance of the front side is lower than that of the back side, and the optical density becomes 3.0 or more. The film thicknesses of the first reflection suppression layer, the light shielding layer, and the second reflection suppression layer. 如請求項1之光罩基底，其中上述第1反射抑制層及上述第2反射抑制層分別具有氧及氮中至少一個元素之含有率沿著膜厚方向而連續地或階段性地有組成變化之區域。The photomask substrate of claim 1, wherein the first reflection suppressing layer and the second reflection suppressing layer respectively have at least one element of oxygen and nitrogen. The content of at least one element of oxygen and nitrogen is continuously or stepwise changed in composition along the film thickness direction的区。 The area. 如請求項1或2之光罩基底，其中上述第2反射抑制層具有朝向膜厚方向之上述遮光層側而氧之含有率增加之區域。The photomask substrate of claim 1 or 2, wherein the second reflection suppressing layer has a region where the oxygen content rate increases toward the side of the light shielding layer in the film thickness direction. 如請求項1或2之光罩基底，其中上述第2反射抑制層具有朝向膜厚方向之上述遮光層側而氮之含有率降低之區域。The photomask substrate of claim 1 or 2, wherein the second reflection suppression layer has a region where the nitrogen content is reduced toward the side of the light shielding layer in the film thickness direction. 如請求項1或2之光罩基底，其中上述第1反射抑制層具有朝向膜厚方向之上述透明基板而氧之含有率增加並且氮之含有率降低之區域。The photomask substrate of claim 1 or 2, wherein the first reflection suppressing layer has a region where the transparent substrate faces the film thickness direction and the oxygen content rate increases and the nitrogen content rate decreases. 如請求項1或2之光罩基底，其中上述第2反射抑制層係以氧之含有率較上述第1反射抑制層變高之方式構成。The photomask substrate of claim 1 or 2, wherein the second reflection suppressing layer is formed in such a way that the content of oxygen becomes higher than that of the first reflection suppressing layer. 如請求項1或2之光罩基底，其中上述遮光層包含鉻(Cr)與氮化二鉻(Cr2 N)。The mask substrate of claim 1 or 2, wherein the light-shielding layer includes chromium (Cr) and chromium nitride (Cr 2 N). 如請求項1或2之光罩基底，其中上述第1反射抑制層及上述第2反射抑制層包含氮化鉻(CrN)、氧化鉻(III)(Cr2 O3 )及氧化鉻(VI)(CrO3 )。The mask substrate of claim 1 or 2, wherein the first reflection suppression layer and the second reflection suppression layer include chromium nitride (CrN), chromium (III) oxide (Cr 2 O 3 ), and chromium oxide (VI) (CrO 3 ). 如請求項1或2之光罩基底，其中於上述透明基板與上述遮光膜之間，進而具備具有較上述遮光膜之光學濃度低之光學濃度的半透光膜。The mask base of claim 1 or 2, wherein between the transparent substrate and the light-shielding film, there is further provided a semi-transmissive film having an optical density lower than that of the light-shielding film. 如請求項1或2之光罩基底，其中於上述透明基板與上述遮光膜之間進而具備相位偏移膜。The photomask base of claim 1 or 2, wherein a phase shift film is further provided between the transparent substrate and the light-shielding film. 一種光罩之製造方法，其特徵在於具有如下步驟： 準備如請求項1至10中任一項之上述光罩基底；及 於上述遮光膜上形成抗蝕劑膜，將自上述抗蝕劑膜形成之抗蝕劑圖案作為遮罩對上述遮光膜進行蝕刻而於上述透明基板上形成遮光膜圖案。A method for manufacturing a photomask, which is characterized by the following steps: Prepare the above-mentioned photomask substrate as in any one of Claims 1 to 10; and A resist film is formed on the light-shielding film, and the light-shielding film is etched using the resist pattern formed from the resist film as a mask to form a light-shielding film pattern on the transparent substrate. 一種光罩之製造方法，其特徵在於具有如下步驟： 準備如請求項9之上述光罩基底； 於上述遮光膜上形成抗蝕劑膜，將自上述抗蝕劑膜形成之抗蝕劑圖案作為遮罩對上述遮光膜進行蝕刻而於上述半透光膜上形成遮光膜圖案；及 將上述遮光膜圖案作為遮罩對上述半透光膜進行蝕刻而於上述透明基板上形成半透光膜圖案。A method for manufacturing a photomask, which is characterized by the following steps: Prepare the above-mentioned mask substrate as in claim 9; Forming a resist film on the light-shielding film, etching the light-shielding film using the resist pattern formed from the resist film as a mask to form a light-shielding film pattern on the semi-transmissive film; and The translucent film is etched using the light-shielding film pattern as a mask to form a translucent film pattern on the transparent substrate. 一種光罩之製造方法，其特徵在於具有如下步驟： 準備如請求項10之上述光罩基底； 於上述遮光膜上形成抗蝕劑膜，將自上述抗蝕劑膜形成之抗蝕劑圖案作為遮罩對上述遮光膜進行蝕刻而於上述相位偏移膜上形成遮光膜圖案；及 將上述遮光膜圖案作為遮罩對上述相位偏移膜進行蝕刻而於上述透明基板上形成相位偏移膜圖案。A method for manufacturing a photomask, which is characterized by the following steps: Prepare the above-mentioned mask substrate as in claim 10; Forming a resist film on the light-shielding film, etching the light-shielding film using the resist pattern formed from the resist film as a mask to form a light-shielding film pattern on the phase shift film; and The phase shift film is etched using the light-shielding film pattern as a mask to form a phase shift film pattern on the transparent substrate. 如請求項11至13中任一項之光罩之製造方法，其中上述光罩中，上述遮光膜為TFT陣列中之閘極電極或源極電極/汲極電極之配線圖案。The method for manufacturing a photomask according to any one of claims 11 to 13, wherein in the photomask, the light-shielding film is a wiring pattern of a gate electrode or a source electrode/drain electrode in a TFT array. 如請求項11至13中任一項之光罩之製造方法，其中上述光罩中，上述遮光膜圖案之開口率為50%以上。The method for manufacturing a photomask according to any one of claims 11 to 13, wherein in the photomask, the aperture ratio of the light-shielding film pattern is 50% or more. 一種顯示裝置之製造方法，其特徵在於具有曝光步驟，該曝光步驟係將藉由如請求項11至15中任一項之光罩之製造方法而獲得之光罩載置於曝光裝置之遮罩載台，將形成於上述光罩上之上述遮光膜圖案之遮罩圖案曝光轉印至形成於顯示裝置基板上之抗蝕劑。A method for manufacturing a display device, characterized by having an exposure step, the exposure step is to place a mask obtained by the method for manufacturing a mask according to any one of claims 11 to 15 on the mask of the exposure device The stage exposes and transfers the mask pattern of the light-shielding film pattern formed on the photomask to the resist formed on the substrate of the display device.
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