TWI417645B - Mask mask and mask, and its manufacturing methods - Google Patents
Mask mask and mask, and its manufacturing methods Download PDFInfo
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- TWI417645B TWI417645B TW096106700A TW96106700A TWI417645B TW I417645 B TWI417645 B TW I417645B TW 096106700 A TW096106700 A TW 096106700A TW 96106700 A TW96106700 A TW 96106700A TW I417645 B TWI417645 B TW I417645B
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
- G03F1/54—Absorbers, e.g. of opaque materials
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
- G03F1/38—Masks having auxiliary features, e.g. special coatings or marks for alignment or testing; Preparation thereof
- G03F1/46—Antireflective coatings
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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
- G03F1/68—Preparation processes not covered by groups G03F1/20 - G03F1/50
- G03F1/80—Etching
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
- H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
- H01L21/0274—Photolithographic processes
- H01L21/0276—Photolithographic processes using an anti-reflective coating
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/033—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers
- H01L21/0332—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers characterised by their composition, e.g. multilayer masks, materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/033—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers
- H01L21/0334—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers characterised by their size, orientation, disposition, behaviour, shape, in horizontal or vertical plane
- H01L21/0337—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers characterised by their size, orientation, disposition, behaviour, shape, in horizontal or vertical plane characterised by the process involved to create the mask, e.g. lift-off masks, sidewalls, or to modify the mask, e.g. pre-treatment, post-treatment
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- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Preparing Plates And Mask In Photomechanical Process (AREA)
- Physical Vapour Deposition (AREA)
Description
本發明係關於使遮光膜之濕式蝕刻特性最適於用以形成遮光膜圖案之濕式蝕刻處理的光罩毛胚及光罩，暨其等製造方法。尤其係關於用以製造FPD元件之光罩毛胚、及使用該光罩毛胚所製造之光罩。The present invention relates to a reticle blank and a photomask which are suitable for wet etching treatment of a light shielding film pattern, and a manufacturing method thereof. In particular, it relates to a reticle blank for manufacturing an FPD element, and a reticle manufactured using the reticle blank.
一般而言，於半導體裝置及液晶顯示裝置之製造步驟中，使用光微影法來形成微細圖案，形成該微細圖案時通常使用稱為光罩之基板，一般而言，該光罩係於透光性玻璃基板上設置有由金屬薄膜等所構成之遮光性微細圖案者，製造該光罩時亦使用光微影法。Generally, in the manufacturing steps of a semiconductor device and a liquid crystal display device, a fine pattern is formed by photolithography, and when the fine pattern is formed, a substrate called a photomask is generally used. Generally, the photomask is transparent. A light-shielding fine pattern formed of a metal thin film or the like is provided on the optical glass substrate, and a photolithography method is also used in the production of the photomask.
利用光微影法製造光罩時，可使用在玻璃基板等透光性基板上具有遮光膜之光罩毛胚。使用該光罩毛胚製造光罩包括下述步驟：曝光步驟，對形成於光罩毛胚上之光阻膜實施所期望之圖案曝光；顯影步驟，隨著所期望之圖案曝光使上述光阻膜顯影而形成光阻圖案；蝕刻步驟，沿著光阻圖案對上述遮光膜進行蝕刻；及剝離除去殘存光阻圖案之步驟。於上述顯影步驟中，對形成於光罩毛胚上之光阻膜實施所期望之圖案曝光後供給顯影液，溶解可溶於顯影液之光阻膜部位，而形成光阻圖案。另外，於上述蝕刻步驟中，將該光阻圖案作為遮罩，例如，藉由濕式蝕刻，溶解未形成有光阻圖案之遮光膜所露出之部位，藉此於透光性基板上形成所期望之遮罩圖案。如此可製成光罩。When the photomask is produced by the photolithography method, a photomask blank having a light shielding film on a light transmissive substrate such as a glass substrate can be used. The use of the reticle blank to fabricate the reticle comprises the steps of: exposing the desired pattern exposure to the photoresist film formed on the reticle blank; developing step, exposing the photoresist to the desired pattern The film is developed to form a photoresist pattern; an etching step is performed to etch the light shielding film along the photoresist pattern; and a step of removing the remaining photoresist pattern is performed. In the above development step, the photoresist film formed on the reticle blank is subjected to a desired pattern exposure, and then supplied to the developer to dissolve the photoresist film portion soluble in the developer to form a photoresist pattern. Further, in the etching step, the photoresist pattern is used as a mask, and for example, by wet etching, a portion of the light-shielding film in which the photoresist pattern is not formed is dissolved, thereby forming a portion on the light-transmitting substrate. The desired mask pattern. This makes it possible to make a photomask.
於日本專利特公昭62－32782號公報中，作為適於濕式蝕刻之遮罩毛胚，揭示有於透明基板上具備含有鉻碳化物之鉻膜作為遮光膜之光罩毛胚。另外，於日本專利第2983020號公報中，同樣，作為適於濕式蝕刻之遮罩毛胚，揭示有下述半色調型相移遮罩毛胚，該遮罩毛胚於透明基板上具有半色調材料膜與金屬膜之積層膜，該金屬膜中，自表面側向透明基板側存在由蝕刻率不同之材料所構成之區域，並且該半色調型相移遮罩毛胚包含例如CrN/CrC金屬膜及CrON抗反射膜。In the mask blank suitable for wet etching, a mask blank having a chrome film containing chromium carbide as a light-shielding film on a transparent substrate is disclosed in Japanese Patent Publication No. Sho 62-32782. Further, in Japanese Patent No. 2983020, similarly, as a mask blank suitable for wet etching, the following halftone type phase shift mask blank is disclosed, and the mask blank has a half on a transparent substrate. a laminated film of a color material film and a metal film, wherein a region composed of a material having a different etching rate exists from the surface side toward the transparent substrate side, and the halftone phase shift mask blank contains, for example, CrN/CrC Metal film and CrON anti-reflection film.
然而，製造液晶顯示裝置中之例如彩色濾光器、TFT薄膜電晶體陣列、或反射板等零件時所使用之光罩，係相較於LSI用光罩其基板尺寸大。因此，由於基板尺寸較大，故與基板尺寸較小之情況相比具有下述特點，即，由於製造原理上之限制(來自製造方法或製造裝置之限制)之主要原因、以及製造條件之變動(製程變動)之主要原因，而容易於面內及基板間產生各特性(膜組成、膜質、透射率、反射率、光學濃度、蝕刻特性、其他光學特性、膜厚等)之不均一，因此無法獲得面內及基板間之各特性均一之零件。此種特點存在隨著FPD平板顯示器之進一步大型化、高精細化而增長之傾向。However, the photomask used in the manufacture of a component such as a color filter, a TFT thin film transistor array, or a reflector in a liquid crystal display device has a larger substrate size than the LSI photomask. Therefore, since the substrate is large in size, it has the following characteristics as compared with the case where the substrate size is small, that is, the main reason for the limitation of manufacturing principle (from the limitation of the manufacturing method or the manufacturing apparatus), and variations in manufacturing conditions. (The process variation) is mainly caused by the inconsistency between the in-plane and the substrate (film composition, film quality, transmittance, reflectance, optical density, etching characteristics, other optical characteristics, film thickness, etc.). Parts with uniform characteristics between the in-plane and the substrate are not available. Such a tendency tends to increase as the FPD flat panel display is further enlarged and refined.
近年來，隨著液晶顯示裝置之高精細化，雖然形成於光罩之圖案之最小線寬為2~3 μm左右，但已微細化至1 μm左右以下。於此種狀況下，存在其他尺寸精度(線寬公差、總間距精度，重合精度)亦變嚴格之傾向。In recent years, with the high definition of the liquid crystal display device, the minimum line width of the pattern formed on the photomask is about 2 to 3 μm, but it has been reduced to about 1 μm or less. Under such conditions, other dimensional accuracy (line width tolerance, total pitch accuracy, coincidence accuracy) tends to be stricter.
另外，如此使液晶顯示裝置之圖案高精細化，須要對經微細化之遮罩圖案進行精度良好之圖案轉印。為此，較理想為，形成於大型基板整個面上之遮罩圖案中未產生模糊，且剖面形狀良好。例如，較理想為，形成於光罩上之遮罩圖案之剖面形狀為大致與膜面垂直之形狀。Further, in order to refine the pattern of the liquid crystal display device in this manner, it is necessary to perform pattern transfer with high precision on the mask pattern which is miniaturized. For this reason, it is preferable that no blur occurs in the mask pattern formed on the entire surface of the large substrate, and the cross-sectional shape is good. For example, it is preferable that the cross-sectional shape of the mask pattern formed on the photomask is a shape substantially perpendicular to the film surface.
習知，就成為製造液晶顯示裝置所使用之光罩之原版的光罩毛胚而言，一直使用在玻璃基板上形成有使氧化鉻(CrO)膜及鉻(Cr)膜積層而成之遮光膜的光罩毛胚，或在玻璃基板上形成有使氧化鉻(CrO)膜、鉻(Cr)膜及氧化鉻(CrO)膜積層而成之遮光膜的光罩毛胚。另外，上述氧化鉻(CrO)膜係具有使膜面對曝光之光之反射降低的抗反射功能之抗反射膜。Conventionally, as a mask blank for manufacturing a master of a photomask used in a liquid crystal display device, it has been conventionally used to form a light-shielding layer formed by laminating a chromium oxide (CrO) film and a chromium (Cr) film on a glass substrate. A mask blank of a film or a mask blank in which a light-shielding film formed by laminating a chromium oxide (CrO) film, a chromium (Cr) film, and a chromium oxide (CrO) film is formed on a glass substrate. Further, the chromium oxide (CrO) film described above has an antireflection film having an antireflection function for reducing the reflection of the film toward the exposed light.
並且，使用硝酸鈰銨、過氯酸及純水之蝕刻劑，將形成於遮光膜上之光阻圖案作為遮罩，利用濕式蝕刻使上述光罩毛胚形成遮光膜圖案，製作光罩。Then, using a photoresist pattern of cerium ammonium nitrate, perchloric acid, and pure water, the photoresist pattern formed on the light-shielding film was used as a mask, and the mask blank was formed into a light-shielding film pattern by wet etching to prepare a photomask.
然而，在近年來光罩圖案逐步微細化之狀況下，習知之遮光膜產生下述問題，即，無法忽視遮罩圖案之模糊(俯視遮罩圖案時之圖案邊緣粗糙度(圖案邊緣之凹部與凸部之最大距離))，另外，無法獲得剖面形狀良好(垂直)之圖案。該遮罩圖案中之模糊或圖案之剖面形狀，於使用光罩製作液晶顯示裝置時成為引起顯示不均之原因。However, in the case where the mask pattern is gradually miniaturized in recent years, the conventional light-shielding film has a problem that the blur of the mask pattern cannot be ignored (the edge roughness of the pattern when the mask pattern is viewed (the concave portion of the pattern edge and The maximum distance of the convex portion)), in addition, a pattern in which the cross-sectional shape is good (vertical) cannot be obtained. The blurring of the mask pattern or the cross-sectional shape of the pattern causes a display unevenness when the liquid crystal display device is fabricated using a photomask.
因此，本發明係為解決習知問題而開發完成者，其目的在於提供藉由使遮光膜之濕式蝕刻特性最佳化而可形成剖面形狀良好之遮光膜圖案，進而可形成圖案之模糊極小之遮光膜圖案的光罩毛胚及光罩，暨其等製造方法。Therefore, the present invention has been developed to solve the conventional problems, and an object of the present invention is to provide a light-shielding film pattern having a good cross-sectional shape by optimizing the wet etching characteristics of the light-shielding film, thereby further minimizing the pattern formation. The mask blank and the mask of the light-shielding film pattern, and the manufacturing method thereof.
如前文所述，習知由於遮光膜之膜厚、或遮光膜之深度方向上之組成傾斜等限制，而難以對藉由濕式蝕刻處理形成之遮光膜圖案之剖面形狀進行良好加工，鑒於上述問題，本發明者進行仔細研究的結果發現，查明構成鉻系遮光膜之鉻之結晶性與遮光膜之濕式蝕刻特性存在相關關係，進而，藉由控制該鉻之結晶性來控制遮光膜之濕式蝕刻特性，結果為，可進行控制使遮光膜圖案之剖面形狀成為良好形狀，另外，圖案模糊變得極小。As described above, it is conventionally difficult to perform a good processing of the cross-sectional shape of the light-shielding film pattern formed by the wet etching process due to limitations such as the film thickness of the light-shielding film or the composition tilt in the depth direction of the light-shielding film, in view of the above. The inventors of the present invention have conducted intensive studies and found that the crystallinity of the chromium constituting the chromium-based light-shielding film is correlated with the wet etching property of the light-shielding film, and further, the light-shielding film is controlled by controlling the crystallinity of the chromium. As a result of the wet etching property, it is possible to control so that the cross-sectional shape of the light-shielding film pattern is a good shape, and the pattern blurring is extremely small.
即，為解決上述課題，本發明具有以下構成。That is, in order to solve the above problems, the present invention has the following configuration.
(構成1)一種光罩毛胚，其係於透光性基板上具有遮光膜者，其特徵為，上述光罩毛胚係將形成於上述遮光膜上之遮罩圖案作為遮罩，且藉由濕式蝕刻處理而使上述遮光膜圖案化的光罩之製作方法所對應之濕式蝕刻處理用光罩毛胚，上述遮光膜包含含鉻材料，且，根據X射線繞射之CrN(200)之繞射峰值所算出之微晶尺寸為10 nm以下。(Configuration 1) A reticle blank having a light-shielding film on a light-transmitting substrate, wherein the reticle blank has a mask pattern formed on the light-shielding film as a mask, and A mask blank for wet etching treatment corresponding to a method of producing a mask for patterning the light-shielding film by wet etching, wherein the light-shielding film contains a chromium-containing material, and CrN (200 according to X-ray diffraction) The crystallite size calculated by the diffraction peak is 10 nm or less.
(構成2)如構成1所述之光罩毛胚，其中，上述遮光膜係藉由X射線繞射法所獲得之繞射峰值具有CrN(200)之繞射峰值及Cr(110)之繞射峰值之薄膜。(Claim 2) The reticle blank according to the first aspect, wherein the light-shielding film has a diffraction peak obtained by an X-ray diffraction method and has a diffraction peak of CrN (200) and a winding of Cr (110). A film that shoots a peak.
(構成3)如構成1或2所述之光罩毛胚，其中，上述遮光膜於深度方向之大致所有區域上含有氮(N)。(Aspect 3) The reticle blank according to the first or second aspect, wherein the light-shielding film contains nitrogen (N) in substantially all regions in the depth direction.
(構成4)如構成1至3中任一項所述之光罩毛胚，其中，於上述遮光膜之上層部形成含有氧之抗反射層。The reticle blank according to any one of the above 1 to 3, wherein the antireflection layer containing oxygen is formed on the upper layer portion of the light shielding film.
(構成5)如構成1至4中任一項所述之光罩毛胚，其中，上述光罩毛胚係用以製造FPD元件之光罩毛胚。The reticle blank according to any one of the preceding claims, wherein the reticle blank is used to manufacture a reticle blank of an FPD element.
(構成6)一種光罩，其特徵為，藉由濕式蝕刻處理使構成1至5中任一項所述之光罩毛胚中之上述遮光膜圖案化，於上述透光性基板上形成遮光膜圖案。(Configuration 6) A photomask characterized by patterning the light-shielding film in the reticle blank according to any one of 1 to 5 by wet etching to form on the light-transmissive substrate Light-shielding film pattern.
(構成7)一種光罩毛胚之製造方法，其包括下述步驟，藉由使用有包含含鉻材料之靶材的濺鍍成膜，而於透光性基板上形成含鉻遮光膜，其特徵為，上述光罩毛胚係將形成於上述遮光膜上之光阻圖案作為遮罩，且藉由濕式蝕刻處理使上述遮光膜圖案化的光罩之製作方法所對應之濕式蝕刻處理用光罩毛胚，上述光罩毛胚之製造方法控制構成上述遮光膜之鉻之結晶性，以使藉由上述濕式蝕刻處理而形成之遮光膜圖案之剖面形狀成為既定形狀。(Configuration 7) A method for producing a reticle blank, comprising the steps of forming a chrome-containing light-shielding film on a light-transmitting substrate by using a sputtering film having a target material containing a chromium-containing material The photomask blank is characterized in that the photoresist pattern formed on the light-shielding film is used as a mask, and the wet etching process corresponding to the method of fabricating the light-shielding film patterned by the wet etching process In the reticle blank, the method for producing the reticle blank controls the crystallinity of the chrome constituting the light-shielding film so that the cross-sectional shape of the light-shielding film pattern formed by the wet etching treatment has a predetermined shape.
(構成8)如構成7所述之光罩毛胚之製造方法，其中，形成上述遮光膜後，藉由調整施加於該遮光膜之熱處理條件，而控制構成上述遮光膜之鉻之結晶性。(Attachment 8) The method for producing a reticle blank according to the seventh aspect, wherein, after the light shielding film is formed, the crystallinity of chromium constituting the light shielding film is controlled by adjusting heat treatment conditions applied to the light shielding film.
(構成9)如構成7或8所述之光罩毛胚之製造方法，其中，上述熱處理係於上述遮光膜上形成光阻膜前、或形成光阻膜後之加熱處理。(Aspect 9) The method for producing a reticle blank according to the seventh or eighth aspect, wherein the heat treatment is a heat treatment before forming a photoresist film on the light-shielding film or after forming a photoresist film.
(構成10)如構成7至9中任一項所述之光罩毛胚之製造方法，其中，藉由上述濕式蝕刻處理所形成之遮光膜圖案之剖面形狀係相對於膜面呈大致垂直之形狀。The method of manufacturing a reticle blank according to any one of the items 7 to 9, wherein the cross-sectional shape of the light-shielding film pattern formed by the wet etching treatment is substantially perpendicular to the film surface. The shape.
(構成11)如構成7至10中任一項所述之光罩毛胚之製造方法，其中，上述光罩毛胚係用以製造FPD元件之光罩毛胚。The method of manufacturing a reticle blank according to any one of the items 7 to 10, wherein the reticle blank is used to manufacture a reticle blank of an FPD element.
(構成12)一種光罩之製造方法，其特徵為包括下述步驟，藉由濕式蝕刻處理，使藉由構成7至11中任一項所述之製造方法而獲得之光罩毛胚中之上述遮光膜圖案化。(Construction 12) A method of manufacturing a photomask, comprising the steps of: forming a reticle blank obtained by the manufacturing method according to any one of 7 to 11 by a wet etching treatment The above light shielding film is patterned.
如構成1所述，本發明之光罩毛胚係於透光性基板上具有遮光膜者，上述光罩毛胚係將形成於上述遮光膜上之遮罩圖案作為遮罩，且藉由濕式蝕刻處理使上述遮光膜圖案化的光罩之製作方法所對應之濕式蝕刻處理用光罩毛胚，上述遮光膜包含含鉻材料，且根據X射線繞射之CrN(200)之繞射峰值所算出之微晶尺寸為10 nm以下。As described in the first aspect, the reticle blank of the present invention has a light-shielding film on the light-transmitting substrate, and the reticle blank has a mask pattern formed on the light-shielding film as a mask, and is wet. An etching process for a wet etching process reticle corresponding to a method of fabricating a mask for patterning the light-shielding film, wherein the light-shielding film comprises a chrome-containing material and is circulated by a X-ray diffraction CrN (200) The crystallite size calculated from the peak is 10 nm or less.
如此，對於遮光膜之結晶性，使根據CrN(200)之繞射峰值所算出之微晶尺寸為10 nm以下，藉此，於利用濕式蝕刻使遮光膜圖案化時，可極其減小遮光膜圖案之模糊，進而，遮光膜圖案之剖面形狀可成為良好形狀。就減小上述遮光膜圖案之模糊之方面而言，較佳為使根據CrN(200)之繞射峰值所算出之微晶尺寸更小，然而，就遮光膜圖案之剖面形狀或成膜速度等生產性而言，微晶尺寸過小亦不佳。考慮到上述方面，較佳為根據CrN(200)之繞射峰值所算出之微晶尺寸為5 nm以上、10 nm以下。As described above, the crystallinity of the light-shielding film is such that the crystallite size calculated from the diffraction peak of CrN (200) is 10 nm or less, whereby the pattern can be extremely reduced when the light-shielding film is patterned by wet etching. The film pattern is blurred, and further, the cross-sectional shape of the light-shielding film pattern can be a good shape. In terms of reducing the blurring of the light-shielding film pattern, it is preferable to make the crystallite size calculated from the diffraction peak of CrN (200) smaller, however, the cross-sectional shape or film formation speed of the light-shielding film pattern, etc. In terms of productivity, the crystallite size is too small and not good. In view of the above, it is preferred that the crystallite size calculated from the diffraction peak of CrN (200) is 5 nm or more and 10 nm or less.
另外，如構成2所述，由於利用X射線繞射法所獲得之繞射峰值具有CrN(200)之繞射峰值及Cr(110)之繞射峰值，而可易於控制遮光膜圖案之形狀，故為佳。Further, as described in the configuration 2, since the diffraction peak obtained by the X-ray diffraction method has a diffraction peak of CrN (200) and a diffraction peak of Cr (110), the shape of the light shielding film pattern can be easily controlled. Therefore, it is better.
另外，如構成3所述，藉由使遮光膜為在深度方向的整個區域上含有氮(N)之膜，可提高濕式蝕刻速度，與形成於遮光膜上之光阻膜之薄膜化相對應，因此可形成更微細且高精細之遮光膜圖案。Further, as described in the third aspect, by providing the light-shielding film with a film containing nitrogen (N) over the entire depth direction, the wet etching rate can be increased, and the thin film formation phase of the photoresist film formed on the light-shielding film can be improved. Correspondingly, a finer and finer light-shielding film pattern can be formed.
另外，如構成4所述，上述遮光膜可於其上層部形成含氧之抗反射層。藉由形成此種抗反射層，可將曝光波長中之反射率抑制為低反射率，因此將遮罩圖案轉印至被轉印體時可抑制與投影曝光面之間的多重反射，從而可抑制成像特性之下降。Further, as described in the configuration 4, the light-shielding film may form an oxygen-containing anti-reflection layer in the upper portion thereof. By forming such an anti-reflection layer, the reflectance in the exposure wavelength can be suppressed to a low reflectance, so that the multiple reflection between the projection and the exposure surface can be suppressed when the mask pattern is transferred to the object to be transferred. Suppresses the degradation of imaging characteristics.
另外，如構成5所述，上述光罩毛胚適用於用以製造FPD元件之光罩毛胚，上述FPD元件為大型基板，且於基板整個面要求遮光膜圖案之尺寸精度。Further, as described in the fifth aspect, the reticle blank is applied to a reticle blank for manufacturing an FPD element, and the FPD element is a large substrate, and the dimensional accuracy of the light shielding film pattern is required over the entire surface of the substrate.
另外，如構成6所述，可成為下述良好之光罩，該光罩藉由濕式蝕刻處理使構成1至5中任一項所述之光罩毛胚中之上述遮光膜圖案化而形成之遮光膜圖案，其剖面形狀良好，且遮光膜圖案之模糊極小。Further, as described in the configuration 6, the light-shielding film can be patterned by the wet etching process by patterning the light-shielding film in the reticle blank of any one of the first to fifth embodiments. The formed light-shielding film pattern has a good cross-sectional shape, and the blur of the light-shielding film pattern is extremely small.
另外，如構成7所述，光罩毛胚之製造方法包括藉由使用包含含鉻材料之靶材所進行的濺鍍成膜，而於透光性基板上形成含鉻遮光膜之步驟，而上述光罩毛胚係將形成於上述遮光膜上之光阻圖案作為遮罩，且藉由濕式蝕刻處理使上述遮光膜圖案化的光罩之製作方法所對應之濕式蝕刻處理用光罩毛胚，因此，以使藉由上述濕式蝕刻處理所形成之遮光膜圖案之剖面形狀成為既定形狀之方式，控制構成上述遮光膜之鉻之結晶性。Further, as described in the configuration 7, the method of manufacturing the reticle blank includes the step of forming a chrome-containing light-shielding film on the light-transmitting substrate by sputtering using a target comprising a chromium-containing material, and The mask blank is a mask for wet etching treatment corresponding to a method of manufacturing a mask for patterning the light-shielding film by using a photoresist pattern formed on the light-shielding film as a mask. In the case of the blank, the crystallinity of the chromium constituting the light-shielding film is controlled so that the cross-sectional shape of the light-shielding film pattern formed by the above-described wet etching treatment has a predetermined shape.
如此，藉由控制遮光膜之結晶性，可控制遮光膜之濕式蝕刻特性，藉此，可進行控制以使遮光膜圖案之剖面形狀成為良好形狀，進而使遮光膜圖案之模糊變得極小。By controlling the crystallinity of the light-shielding film in this manner, the wet etching characteristics of the light-shielding film can be controlled, whereby the cross-sectional shape of the light-shielding film pattern can be controlled to be good, and the blurring of the light-shielding film pattern can be minimized.
例如，如構成8所述，形成上述遮光膜後，藉由對施加於該遮光膜之熱處理條件進行調整，可較佳地控制構成上述遮光膜之鉻之結晶性。For example, as described in the configuration 8, after the light shielding film is formed, the crystallinity of the chromium constituting the light shielding film can be preferably controlled by adjusting the heat treatment conditions applied to the light shielding film.
此處，鉻之結晶性，例如係CrN(200)之微晶尺寸，如構成8所述，較佳為，形成上述遮光膜後，藉由調整施加於該遮光膜之熱處理條件，而控制構成上述遮光膜之鉻之微晶尺寸。Here, the crystallinity of chromium, for example, the crystallite size of CrN (200), as described in the configuration 8, is preferably such that after the light shielding film is formed, the heat treatment conditions applied to the light shielding film are adjusted to control the composition. The crystallite size of the chromium of the above light-shielding film.
另外，如構成9所述，對遮光膜之熱處理係於上述遮光膜上形成光阻膜之前、或形成光阻膜後之加熱處理。一般而言，於光罩毛胚之製造步驟中，於遮光膜形成後，會進行光阻膜形成前所進行之以提高附著力為目的之烘烤處理、或光阻膜形成後之預烘烤處理，因此，較佳為，藉由調整該等加熱處理條件，而控制構成遮光膜之鉻之結晶性(例如，鉻之微晶尺寸)。Further, as described in the configuration 9, the heat treatment of the light-shielding film is performed after the photoresist film is formed on the light-shielding film or after the photoresist film is formed. In general, in the manufacturing step of the reticle blank, after the formation of the light-shielding film, the baking treatment for improving the adhesion before the formation of the photoresist film or the pre-baking after the formation of the photoresist film is performed. Since the baking treatment is performed, it is preferred to control the crystallinity (for example, the crystallite size of chromium) of the chromium constituting the light-shielding film by adjusting the heat treatment conditions.
另外，如構成10所述，藉由上述濕式蝕刻處理而形成之遮光膜圖案之剖面形狀，較理想為相對於膜面呈大致垂直之形狀，因可根據本發明良好地控制遮光膜圖案之剖面形狀，故為較佳。Further, as described in the configuration 10, the cross-sectional shape of the light-shielding film pattern formed by the wet etching treatment is preferably substantially perpendicular to the film surface, because the light-shielding film pattern can be favorably controlled according to the present invention. It is preferred because of the cross-sectional shape.
另外，如構成11所述，上述光罩毛胚適用於用以製造FPD元件之光罩毛胚，上述FPD元件為大型基板，且基板整個面上對遮光膜圖案之尺寸精度有所要求。Further, as described in the configuration 11, the reticle blank is applied to a reticle blank for manufacturing an FPD element, and the FPD element is a large substrate, and the dimensional accuracy of the light shielding film pattern is required on the entire surface of the substrate.
另外，如構成12所述，藉由濕式蝕刻處理使利用構成7至11中任一項所述之製造方法所獲得之光罩毛胚中之上述遮光膜圖案化，利用包括上述步驟之光罩之製造方法可獲得下述良好光罩，該光罩藉由濕式蝕刻處理圖案化而形成之遮光膜圖案之剖面形狀良好，且遮光膜圖案之模糊極小。Further, as described in the configuration 12, the light-shielding film in the reticle blank obtained by the manufacturing method according to any one of the items 7 to 11 is patterned by a wet etching process, and the light including the above steps is used. In the method of manufacturing a cover, a good mask having a cross-sectional shape of a light-shielding film pattern formed by wet etching treatment and having a very small blur of the light-shielding film pattern can be obtained.
根據本發明，可提供下述光罩毛胚，將遮光膜之結晶性之根據CrN(200)繞射峰值所算出之微晶尺寸為10 nm以下，藉此可使遮光膜之濕式蝕刻特性最佳化，使遮光膜圖案之剖面形狀成為良好形狀，進而亦可使遮光膜圖案之模糊變得極小。According to the present invention, it is possible to provide a photomask blank in which the crystallinity of the light-shielding film is 10 nm or less in accordance with the diffraction peak of CrN (200), whereby the wet etching property of the light-shielding film can be obtained. Optimized, the cross-sectional shape of the light-shielding film pattern is made into a good shape, and the blurring of the light-shielding film pattern can be made extremely small.
另外，可提供下述光罩，該光罩使用濕式蝕刻處理使利用本發明所獲得之光罩毛胚中之遮光膜圖案化，以此可形成剖面形狀良好、且圖案模糊極小之良好遮光膜圖案。Further, it is possible to provide a photomask which is patterned by using a wet etching process to pattern a light-shielding film in the reticle blank obtained by the present invention, thereby forming a good shading having a good cross-sectional shape and minimal pattern blur. Membrane pattern.
以下，參照圖式，詳細敍述本發明之實施形態。Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
圖1係表示本發明中之光罩毛胚之第一實施形態之剖面圖。BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing a first embodiment of a reticle blank of the present invention.
圖1之光罩毛胚10係用以製作於透光性基板1上具有遮光膜2之FPD的光罩毛胚之形態。The reticle blank 10 of Fig. 1 is used to form a reticle blank having a FPD of the light-shielding film 2 on the light-transmitting substrate 1.
上述光罩毛胚10係將形成於上述遮光膜2上之光阻圖案作為遮罩，且藉由濕式蝕刻處理使上述遮光膜2圖案化的光罩之製作方法所對應之濕式蝕刻處理用光罩毛胚，另外，上述遮光膜2係藉由使用含鉻靶材的濺鍍成膜而形成於透光性基板1上之含鉻遮光膜。The reticle blank 10 is a wet etching process corresponding to a method of manufacturing a reticle in which the light-shielding film 2 is patterned by a wet etching process using a photoresist pattern formed on the light-shielding film 2 as a mask. The mask blank is used, and the light-shielding film 2 is a chromium-containing light-shielding film formed on the light-transmitting substrate 1 by sputtering using a chromium-containing target.
此處，作為透光性基板1，一般為玻璃基板。玻璃基板由於平坦度及平滑度優良，故於使用光罩向被轉印基板上進行圖案轉印時，不會產生轉印圖案之應變等而能進行高精度之圖案轉印。Here, the light-transmitting substrate 1 is generally a glass substrate. Since the glass substrate is excellent in flatness and smoothness, when pattern transfer is performed on the substrate to be transferred using the photomask, pattern transfer or the like of the transfer pattern is not generated, and pattern transfer with high precision can be performed.
於本發明中，上述遮光膜2中，對於構成上述遮光膜2之鉻之結晶性，使根據GrN(200)之繞射峰值所算出之微晶尺寸為10 nm以下，以使藉由濕式蝕刻處理而形成之遮光膜圖案之模糊極小，且使剖面形狀成為既定形狀。進而，較佳為，為提高遮光膜圖案之形狀控制性，除上述微晶尺寸以外，亦對構成遮光膜2之鉻之結晶性，使藉由X射線繞射法所獲得之繞射峰值成為CrN(200)之繞射峰值及Cr(110)之繞射峰值。In the present invention, in the light-shielding film 2, the crystallinity of the chromium constituting the light-shielding film 2 is such that the crystallite size calculated from the diffraction peak of GrN (200) is 10 nm or less so that the wet type is used. The light-shielding film pattern formed by the etching treatment has a very small blur and a cross-sectional shape of a predetermined shape. Further, in order to improve the shape controllability of the light-shielding film pattern, in addition to the crystallite size, the crystallinity of the chromium constituting the light-shielding film 2 is preferably such that the diffraction peak obtained by the X-ray diffraction method becomes The diffraction peak of CrN (200) and the diffraction peak of Cr (110).
作成具有此種結晶性之遮光膜2，則可控制遮光膜2之濕式蝕刻特性，藉此，可使遮光膜圖案之剖面形狀良好，且遮光膜圖案之模糊極小。When the light-shielding film 2 having such crystallinity is formed, the wet etching characteristics of the light-shielding film 2 can be controlled, whereby the cross-sectional shape of the light-shielding film pattern can be made good, and the blur of the light-shielding film pattern is extremely small.
構成遮光膜2之鉻之結晶性，例如，可於形成上述遮光膜2後，藉由調整施加於該遮光膜2之熱處理條件而加以控制。The crystallinity of the chromium constituting the light-shielding film 2 can be controlled, for example, by adjusting the heat treatment conditions applied to the light-shielding film 2 after the light-shielding film 2 is formed.
另外，對遮光膜2之熱處理，例如，係於遮光膜2上形成光阻膜之前、或形成光阻膜後之加熱處理。一般而言，於光罩毛胚之製造步驟中，會進行於遮光膜形成後、光阻膜形成前所進行之以提高附著力為目的之烘烤處理，或光阻膜形成後之預烘烤處理。因此，較佳為藉由調整該等之加熱處理條件，而控制構成遮光膜之鉻之結晶性。Further, the heat treatment of the light shielding film 2 is, for example, a heat treatment before the formation of the photoresist film on the light shielding film 2 or after the formation of the photoresist film. In general, in the manufacturing step of the reticle blank, a baking treatment for improving the adhesion after the formation of the light-shielding film and before the formation of the photoresist film, or pre-baking after the formation of the photoresist film is performed. Baked. Therefore, it is preferred to control the crystallinity of the chromium constituting the light-shielding film by adjusting the heat treatment conditions.
對於遮光膜2之結晶性，使根據X射線繞射之CrN(200)之繞射峰值所算出之微晶尺寸為10 nm以下，進而藉由X射線繞射法所獲得之繞射峰值具有CrN(200)之繞射峰值及Cr(110)之繞射峰值，為了製成具有上述性質之膜，而使遮光膜2為至少含有鉻及氮之材料，更佳為含有鉻、氮、及碳之材料，進一步更佳為含有鉻、氮、碳、及氧之材料；就加熱處理條件而言，於80℃以上、180℃以下，較佳為100℃以上、150℃以下之加熱溫度下進行加熱處理。With respect to the crystallinity of the light-shielding film 2, the crystallite size calculated from the diffraction peak of the CrN (200) which is X-ray-diffracted is 10 nm or less, and the diffraction peak obtained by the X-ray diffraction method has CrN. The diffraction peak of (200) and the diffraction peak of Cr (110), in order to form a film having the above properties, the light shielding film 2 is a material containing at least chromium and nitrogen, more preferably containing chromium, nitrogen, and carbon. Further, the material is more preferably a material containing chromium, nitrogen, carbon, and oxygen; and in terms of heat treatment conditions, it is carried out at a heating temperature of 80 ° C or more and 180 ° C or less, preferably 100 ° C or more and 150 ° C or less. Heat treatment.
如前文所述，較理想為，藉由濕式蝕刻處理而形成之遮光膜圖案之剖面形狀相對於膜面呈大致垂直之形狀。根據本發明，可藉由控制遮光膜2之結晶性而控制遮光膜2之濕式蝕刻特性。其結果為，可進行控制以使遮光膜圖案之剖面形狀為上述良好形狀，且使遮光膜圖案之模糊變得極小，故本發明較佳。As described above, it is preferable that the cross-sectional shape of the light-shielding film pattern formed by the wet etching treatment is substantially perpendicular to the film surface. According to the present invention, the wet etching characteristics of the light shielding film 2 can be controlled by controlling the crystallinity of the light shielding film 2. As a result, it is preferable to control so that the cross-sectional shape of the light-shielding film pattern is the above-described good shape and the blurring of the light-shielding film pattern is extremely small.
作為遮光膜2之具體材料，可列舉含有鉻、氮之材料，將遮光膜2中所含有之鉻(Cr)含量設為1時，在深度方向上存在氮(N)含量為0.5以上之區域及氮(N)含量未滿0.5之區域。例如，作為遮光膜，可列舉：將鉻(Cr)含量設為1時自透光性基板側積層氮(N)含量未滿0.5之層、及氮(N)含量為0.5以上之層的積層膜；將鉻(Cr)含量設為1時自透光性基板側積層氮(N)含量為0.5以上之層、氮(N)含量未滿0.5之層、及氮(N)含量為0.5以上之層的積層膜；或將鉻(Cr)含量設為1時自透光性基板側積層氮(N)含量為0.5以上之層、及氮(N)含量未滿0.5之層的積層膜。再者，於遮光膜為積層膜時，遮光膜中所含有之鉻(Cr)或氮(N)既可階段性變化，亦可連續性變化。Specific examples of the light-shielding film 2 include a material containing chromium and nitrogen, and when the chromium (Cr) content contained in the light-shielding film 2 is 1, an area having a nitrogen (N) content of 0.5 or more in the depth direction is present. And the area where the nitrogen (N) content is less than 0.5. For example, when the content of the chromium (Cr) is 1, the layer in which the nitrogen (N) content is less than 0.5 from the light-transmitting substrate side and the layer in which the nitrogen (N) content is 0.5 or more is laminated. a film; when the chromium (Cr) content is 1, a layer having a nitrogen (N) content of 0.5 or more from the light-transmitting substrate side, a layer having a nitrogen (N) content of less than 0.5, and a nitrogen (N) content of 0.5 or more A laminated film of the layer; or a laminated film in which a layer having a nitrogen (N) content of 0.5 or more and a layer having a nitrogen (N) content of less than 0.5 is formed from the side of the light-transmitting substrate when the chromium (Cr) content is set to 1. Further, when the light shielding film is a laminated film, the chromium (Cr) or nitrogen (N) contained in the light shielding film may be changed stepwise or continuously.
另外，於遮光膜2中亦可進一步含有氧、碳、氟等添加元素。Further, the light shielding film 2 may further contain an additive element such as oxygen, carbon or fluorine.
於上述遮光膜之積層膜中，為在製造FPD所使用之330 mm×450 mm以上之大型基板整個面上藉由濕式蝕刻而形成遮罩圖案未產生模糊、剖面形狀良好之遮光膜圖案，較佳為，使遮光膜之材料為含有鉻及氮之材料，且製成將鉻(Cr)含量設為1時自透光性基板側積層氮(N)含量未滿0.5之層、及氮(N)含量為0.5以上之層的積層膜。In the laminated film of the light-shielding film, a light-shielding film pattern in which a mask pattern is not blurred and has a good cross-sectional shape is formed by wet etching on the entire surface of a large substrate of 330 mm × 450 mm or more used for fabricating an FPD. Preferably, the material of the light-shielding film is a material containing chromium and nitrogen, and a layer having a nitrogen (N) content of less than 0.5 from the side of the light-transmitting substrate when the chromium (Cr) content is set to 1, and nitrogen is used. (N) A laminated film of a layer having a content of 0.5 or more.
上述遮光膜2之形成方法無須特別限定，其中可較佳地列舉濺鍍成膜法。利用濺鍍成膜法可形成均勻且固定膜厚之膜，故於本發明中較佳。於透光性基板1上藉由濺鍍成膜法形成上述遮光膜2之情況下，使用鉻(Cr)靶材作為濺鍍靶材，導入腔室內之濺鍍氣體，使用在氬氣或氦氣等惰性氣體中混合有氧、氮、或二氧化碳、一氧化氮等氣體的氣體。使用在氬氣等惰性氣體中混合有氧氣或二氧化碳氣體之濺鍍氣體時，可形成在鉻中含有氧之遮光膜；使用在氬氣等惰性氣體中混合有氮氣之濺鍍氣體時，可形成在鉻中含有氮之遮光膜；另外，使用在氬氣等惰性氣體中混合有一氧化氮氣體之濺鍍氣體時，可形成在鉻中含有氮及氧之遮光膜。另外，使用在氬氣等惰性氣體中混合有甲烷氣體之濺鍍氣體時，可形成在鉻中含有碳之遮光膜。The method for forming the light-shielding film 2 is not particularly limited, and a sputtering film formation method is preferably used. A film having a uniform and fixed film thickness can be formed by a sputtering film formation method, which is preferable in the present invention. When the light-shielding film 2 is formed on the light-transmissive substrate 1 by a sputtering film formation method, a chromium (Cr) target is used as a sputtering target, and a sputtering gas introduced into the chamber is used for argon gas or helium gas. A gas such as oxygen, nitrogen, or a gas such as carbon dioxide or nitrogen monoxide is mixed with an inert gas such as gas. When a sputtering gas in which oxygen or carbon dioxide gas is mixed in an inert gas such as argon gas is used, a light-shielding film containing oxygen in chromium can be formed; and when a sputtering gas containing nitrogen gas is mixed in an inert gas such as argon gas, it can be formed. A light-shielding film containing nitrogen in chromium; and a sputtering gas containing nitrogen gas and oxygen in an inert gas such as argon gas can be used to form a light-shielding film containing nitrogen and oxygen in chromium. Further, when a sputtering gas in which methane gas is mixed in an inert gas such as argon gas is used, a light-shielding film containing carbon in chromium can be formed.
上述遮光膜2之膜厚以光學濃度相對於曝光之光例如為3.0以上之方式進行設定。具體而言，將製造FPD元件時所使用之超高壓水銀燈作為曝光光源時，上述遮光膜2之膜厚較佳為200 nm以下。若膜厚超過200 nm，則存在遮光膜2之基板面內之膜厚不均變大之傾向，導致遮光膜圖案之圖案精度惡化，故不佳。再者，就遮光膜2之膜厚之下限而言，可在能夠獲得所期望之光學濃度的範圍內儘量使之較薄。The film thickness of the light-shielding film 2 is set such that the optical density is, for example, 3.0 or more with respect to the light to be exposed. Specifically, when the ultrahigh pressure mercury lamp used in the production of the FPD element is used as an exposure light source, the thickness of the light shielding film 2 is preferably 200 nm or less. When the film thickness exceeds 200 nm, the film thickness unevenness in the substrate surface of the light-shielding film 2 tends to increase, and the pattern precision of the light-shielding film pattern is deteriorated, which is not preferable. Further, as for the lower limit of the film thickness of the light-shielding film 2, it is possible to make it as thin as possible within a range in which a desired optical density can be obtained.
另外，上述遮光膜2並未限定於上述如積層膜之多層，亦可為單層。例如，於遮光膜2為積層膜時，可使表層部(上層部)具有抗反射功能。於此情況下，作為具有抗反射功能之抗反射層，例如，可較佳地列舉CrO、CrCO、CrNO、CrCON等材料。藉由設置抗反射層，可將曝光波長中之反射率抑制為例如20%以下，較佳為15%以下，因此可抑制將遮罩圖案轉印至被轉印體時與投影曝光面之間的多重反射，從而可抑制成像特性下降。Further, the light shielding film 2 is not limited to the above-mentioned multilayer such as a laminated film, and may be a single layer. For example, when the light shielding film 2 is a laminated film, the surface layer portion (upper layer portion) can have an antireflection function. In this case, as the antireflection layer having an antireflection function, for example, a material such as CrO, CrCO, CrNO, or CrCON can be preferably used. By providing the antireflection layer, the reflectance in the exposure wavelength can be suppressed to, for example, 20% or less, preferably 15% or less, so that the transfer of the mask pattern to the transfer target and the projection exposure surface can be suppressed. Multiple reflections, thereby suppressing degradation of imaging characteristics.
再者，抗反射層亦可視需要而設置於透光性基板側。Further, the antireflection layer may be provided on the side of the light-transmitting substrate as needed.
另外，亦可使上述遮光膜2為下述組成傾斜膜，即，鉻、及例如氧、氮、碳等元素之含量在深度方向上不同，且於表層部之抗反射層、及此外之層(遮光層)中階段性、或連續性地組成傾斜。為使此種遮光膜為組成傾斜膜，較佳之方法例如為在成膜過程中適當切換上述濺鍍成膜時之濺鍍氣體之種類(組成)。Further, the light-shielding film 2 may be an inclined film having a composition in which the content of elements such as oxygen, nitrogen, and carbon are different in the depth direction, and the anti-reflection layer in the surface layer portion and the layer further The (shading layer) is composed of a stepwise or continuous composition. In order to make such a light-shielding film a composition inclined film, a preferable method is, for example, the type (composition) of the sputtering gas when the sputtering film formation is appropriately switched during the film formation process.
另外，光罩毛胚亦可如下述圖2(a)所示，係在上述遮光膜2上形成光阻膜3之形態。為使遮光膜之圖案精度(CD精度)良好，光阻膜3之膜厚較佳為盡可能較薄。光阻膜之膜厚之下限係以下述方式設定，即，將光阻圖案作為遮罩對遮光膜2進行濕式蝕刻時，光阻膜殘存。Further, the mask blank may be formed in the form of the photoresist film 3 on the light-shielding film 2 as shown in FIG. 2(a) below. In order to make the pattern precision (CD precision) of the light-shielding film good, the film thickness of the photoresist film 3 is preferably as thin as possible. The lower limit of the film thickness of the photoresist film is set such that when the photoresist pattern is wet-etched by using the photoresist pattern as a mask, the photoresist film remains.
繼而，就使用圖1所示之光罩毛胚10的光罩之製造方法加以說明。Next, a method of manufacturing the reticle using the reticle blank 10 shown in Fig. 1 will be described.
使用該光罩毛胚10的光罩之製造方法，包括使用濕式蝕刻使光罩毛胚10之遮光膜2圖案化之步驟，具體而言，包括下述步驟：對形成於光罩毛胚10上之光阻膜實施所期望之圖案曝光(圖案描繪)；隨著所期望之圖案曝光使上述光阻膜顯影而形成光阻圖案；沿著光阻圖案蝕刻上述遮光膜；及剝離除去所殘存之光阻圖案。A method of manufacturing a photomask using the reticle blank 10, comprising the step of patterning the light-shielding film 2 of the reticle blank 10 using wet etching, specifically comprising the steps of: forming a reticle blank The photoresist film on the 10 is subjected to desired pattern exposure (pattern drawing); the photoresist film is developed by exposure of the desired pattern to form a photoresist pattern; the light shielding film is etched along the photoresist pattern; Residual photoresist pattern.
圖2係依序表示使用光罩毛胚10之光罩的製造步驟之剖面圖。Fig. 2 is a cross-sectional view showing the manufacturing steps of the reticle using the reticle blank 10 in order.
圖2(a)係表示於圖1之光罩毛胚10之遮光膜2上形成光阻膜3之狀態。再者，作為光阻材料，既可使用正性光阻材料，亦可使用負性光阻材料。Fig. 2(a) shows a state in which the photoresist film 3 is formed on the light-shielding film 2 of the reticle blank 10 of Fig. 1. Further, as the photoresist material, either a positive photoresist material or a negative photoresist material may be used.
繼而，圖2(b)表示對形成於光罩毛胚10上之光阻膜3實施所期望之圖案曝光(圖案描繪)之步驟。圖案曝光係使用雷射描繪裝置等而進行。上述光阻材料係使用具有與雷射相對應之感光性之材料。Next, FIG. 2(b) shows a step of performing desired pattern exposure (pattern drawing) on the photoresist film 3 formed on the reticle blank 10. Pattern exposure is performed using a laser drawing device or the like. The above photoresist material uses a material having a photosensitive property corresponding to a laser.
繼而，圖2(c)表示隨著所期望之圖案曝光使光阻膜3顯影而形成光阻圖案3a之步驟。該步驟中，對形成於光罩毛胚10上之光阻膜3實施所期望之圖案曝光後供給顯影液，溶解可溶於顯影液之光阻膜部位，而形成光阻圖案3a。Next, FIG. 2(c) shows a step of forming the photoresist pattern 3a by developing the photoresist film 3 as the desired pattern is exposed. In this step, the photoresist film 3 formed on the mask blank 10 is subjected to a desired pattern exposure, and then supplied to the developer to dissolve the photoresist film portion soluble in the developer to form the photoresist pattern 3a.
濕式蝕刻時所使用之蝕刻液，一般而言係使用於硝酸鈰銨中加入過氯酸之水溶液。蝕刻液之濃度、溫度或處理時間等濕式蝕刻之條件，係根據遮光膜之圖案剖面特性等而適當設定。The etching solution used in the wet etching is generally used by adding an aqueous solution of perchloric acid to ammonium cerium nitrate. The conditions of the wet etching such as the concentration, temperature, or treatment time of the etching liquid are appropriately set depending on the pattern profile characteristics of the light shielding film and the like.
圖2(e)表示藉由剝離除去所殘存之光阻圖案3a而獲得之光罩20。如此，藉由本發明，可製成高精度地形成有剖面形狀良好之遮光膜圖案的光罩。Fig. 2(e) shows the photomask 20 obtained by peeling off the remaining photoresist pattern 3a. As described above, according to the present invention, it is possible to form a photomask having a light-shielding film pattern having a good cross-sectional shape with high precision.
再者，本發明並非限定於以上說明之實施形態。即，並非限定於在透光性基板上形成遮光膜的所謂二元遮罩用光罩毛胚，亦可為灰色調遮罩用光罩毛胚，該灰色調光罩用光罩毛胚具有在透光性基板上遮擋曝光之光之遮光部、使曝光之光透射之透射部、及作為半透光性區域之灰色調部。灰色調部，既可為以對曝光之光有所期望之透射率之方式而選定材料之半透光性膜，或，亦可為材料與遮光膜相同的曝光之光之解析極限以下之微細遮光膜圖案。形成有半透光性膜圖案之灰色調遮罩，既可為半透光性膜圖案形成於遮光膜圖案之下之半透光性膜下置型灰色調遮罩，亦可為半透光性膜圖案形成於遮光膜圖案之上之半透光性膜上置型灰色調遮罩。Furthermore, the present invention is not limited to the embodiments described above. That is, it is not limited to a so-called binary mask reticle that forms a light-shielding film on a light-transmitting substrate, and may be a gray-mask mask reticle with a reticle blank The light-shielding substrate blocks the light-shielding portion of the exposed light, the transmission portion that transmits the exposed light, and the gray tone portion as the semi-transmissive region. The gray tone portion may be a semi-transmissive film selected from a material having a desired transmittance to the exposed light, or may be a finer than the analytical limit of the exposure light of the same material as the light-shielding film. Light-shielding film pattern. a gray tone mask formed with a semi-transmissive film pattern, which may be a semi-transmissive film pattern formed under the light-shielding film pattern, or a semi-transmissive film. The film pattern is formed on the semi-transmissive film on the light shielding film pattern to form a gray tone mask.
另外，於本發明中，作為透光性基板，一般可列舉玻璃基板，另外可列舉合成石英玻璃基板、鹼石灰玻璃基板、無鹼玻璃基板等。In the present invention, a light-transmitting substrate is generally a glass substrate, and examples thereof include a synthetic quartz glass substrate, a soda-lime glass substrate, and an alkali-free glass substrate.
另外用以製造FPD元件之透光基板，例如，是指330 mm×450 mm至1400 mm×1600 mm之大型尺寸基板。Further, a light-transmitting substrate for manufacturing an FPD element, for example, refers to a large-sized substrate of 330 mm × 450 mm to 1400 mm × 1600 mm.
另外，於本發明中，作為用以製造FPD元件之光罩毛胚及光罩，可列舉用以製造LCD(液晶顯示器)、電漿顯示器、有機EL(電致發光)顯示器等FPD元件之遮罩毛胚及光罩。Further, in the present invention, as a mask blank and a photomask for manufacturing an FPD element, a cover for manufacturing an FPD element such as an LCD (Liquid Crystal Display), a plasma display, or an organic EL (electroluminescence) display can be cited. Cover blank and mask.
此處，LCD製造用遮罩包括製造LCD所必需之所有光罩，例如，包括用以形成TFT(薄膜電晶體)、尤其是TFT通道部及接觸孔部、及低溫多晶矽TFT、彩色濾光器、反射板等之光罩。其他顯示元件製造用遮罩包括製造有機EL(電致發光)顯示器、電漿顯示器等所必需之所有光罩。Here, the mask for LCD manufacturing includes all of the masks necessary for manufacturing the LCD, for example, including TFTs (thin film transistors), particularly TFT channel portions and contact holes, and low-temperature polysilicon TFTs, color filters. , a reflector such as a reflector. Other masks for manufacturing display elements include all of the photomasks necessary for manufacturing an organic EL (electroluminescence) display, a plasma display, and the like.
以下，根據實施例，更加具體地說明本發明之實施形態。並且，就相對於實施例之比較例加以說明。Hereinafter, embodiments of the present invention will be described more specifically based on examples. Further, a comparative example of the embodiment will be described.
於大型玻璃基板(合成石英，厚度為10 mm，尺寸為850 mm×1200 mm)上使用大型連續式濺鍍裝置，使於膜表面上形成有抗反射膜之遮光膜成膜。成膜係指，分別在連續配置於大型連續式濺鍍裝置內之各空間(濺鍍室)內配置Cr靶材後，首先，將Ar氣體及N2 氣體作為濺鍍氣體使CrN膜連續成膜，進而將Ar氣體及CH4 氣體作為濺鍍氣體使CrC膜連續成膜，繼之將Ar氣體及NO氣體作為濺鍍氣體使CrON膜連續成膜，製作出FPD用大型光罩毛胚。遮光膜於超高壓水銀燈之波長的i線(365 nm)至g線(436 nm)下，作成於光學濃度為3.5之膜厚。將形成有遮光膜之玻璃基板載置於加熱板上，於130℃下進行10分鐘加熱處理。對完成加熱處理之遮光膜，藉由拉賽福背向散射分析(RBS)測定深度方向上之氮比例，結果可確認，該遮光膜係自玻璃基板側將鉻(Cr)含量設為1時氮(N)含量未滿0.5之層及氮(N)含量為0.5以上之層的積層膜，且氮自遮光膜之表面側向玻璃基板側連續性減少。A large-scale continuous sputtering apparatus is used on a large glass substrate (synthetic quartz, thickness 10 mm, size 850 mm × 1200 mm) to form a light-shielding film having an anti-reflection film formed on the surface of the film. Film formation means that after the Cr target is placed in each space (sputter chamber) continuously disposed in the large-scale continuous sputtering apparatus, first, the Ar gas and the N 2 gas are used as a sputtering gas to continuously form the CrN film. In the film, the Cr gas film was continuously formed into a film by using Ar gas and CH 4 gas as a sputtering gas, and then the Ar gas and the NO gas were used as a sputtering gas to continuously form a CrON film, thereby producing a large-sized photomask blank for FPD. The light-shielding film was formed at an optical density of 3.5 at an i-line (365 nm) to a g-line (436 nm) of the wavelength of the ultrahigh pressure mercury lamp. The glass substrate on which the light-shielding film was formed was placed on a hot plate, and heat-treated at 130 ° C for 10 minutes. In the light-shielding film which was subjected to the heat treatment, the ratio of nitrogen in the depth direction was measured by Rasei backscattering analysis (RBS), and it was confirmed that the light-shielding film was set to 1 when the chromium (Cr) content was from the glass substrate side. A layered film of a layer having a nitrogen (N) content of less than 0.5 and a layer having a nitrogen (N) content of 0.5 or more, and nitrogen is continuously reduced from the surface side of the light-shielding film to the glass substrate side.
另外，對該遮光膜藉由X射線繞射法測定結晶性。其結果為，可確認所獲得之遮光膜具有CrN(200)之繞射峰值及Cr(110)之繞射峰值，且由CrN(200)之繞射峰值所算出之微晶尺寸為8 nm。再者，微晶尺寸係使用以下所示之謝樂(Scherrer)公式而算出。Further, the light-shielding film was measured for crystallinity by an X-ray diffraction method. As a result, it was confirmed that the obtained light-shielding film had a diffraction peak of CrN (200) and a diffraction peak of Cr (110), and the crystallite size calculated from the diffraction peak of CrN (200) was 8 nm. Further, the crystallite size was calculated using the Scherrer formula shown below.
微晶尺寸(nm)＝0.9 λ/β cos θβ＝(βc 2 －β0 2 )1/2 此處，λ：0.15418 nmβ：繞射峰值之半峰全幅值之校正值(rad)βc ：繞射峰值之半峰全幅值之測定值β0 ：半峰全幅值之裝置常數(0.12°)θ：布拉格(Bragg)角(繞射角2 θ之1/2)。Crystallite size (nm) = 0.9 λ / β cos θβ = (β c 2 - β 0 2 ) 1/2 where λ: 0.15418 nm β: correction value of the full amplitude of the half-peak of the diffraction peak (rad) β c : measured value of the full amplitude of the half peak of the diffraction peak β 0 : device constant of the full width of the half peak (0.12°) θ: Bragg angle (1/2 of the diffraction angle 2 θ).
繼而，使用上述製作之FPD用大型光罩毛胚，進行清洗處理(純水，常溫)後，於上述遮光膜上塗佈雷射描繪用光阻劑(膜厚為1 μm)後，進行加熱處理。接著，對上述雷射描繪用光阻劑雷射描繪既定之圖案後，藉由顯影處理形成光阻圖案，將該光阻圖案作為遮罩，利用濕式蝕刻使遮光膜圖案化，製作具有寬度為5 μm之通常圖案、及寬度為1 μm之灰色調圖案(包括大型FPD用曝光機之解析極限以下之微細遮光圖案及微細透射部之圖案)之FPD用大型光罩。Then, after the cleaning process (pure water, normal temperature) was performed using the large-sized photoreceptor blank for FPD produced above, a laser for photoresist (thickness: 1 μm) was applied onto the light-shielding film, and then heated. deal with. Next, after drawing a predetermined pattern on the laser for laser light for drawing, the photoresist pattern is formed by development processing, and the photoresist pattern is used as a mask, and the light-shielding film is patterned by wet etching to have a width. A large-sized photomask for FPD is a normal pattern of 5 μm and a gray tone pattern having a width of 1 μm (including a pattern of a fine light-shielding pattern and a fine-transmissive portion below the resolution limit of a large-sized FPD exposure machine).
使用掃描型電子顯微鏡(SEM)觀察形成於該FPD用大型光罩上之遮光膜圖案，任意之遮光膜圖案，於平面觀察圖案時之圖案邊緣凹凸(模糊)未滿0.1 μm，皆為良好。另外，FPD用大型光罩面內之圖案線寬均勻性亦良好。進而，觀察遮光膜圖案之剖面形狀，結果剖面形狀垂直，為良好。The light-shielding film pattern formed on the large-sized photomask for the FPD was observed by a scanning electron microscope (SEM), and any of the light-shielding film patterns was used, and the pattern edge unevenness (blur) at the time of planar observation of the pattern was not more than 0.1 μm. In addition, the uniformity of the line width of the pattern in the face of the large mask of the FPD is also good. Further, the cross-sectional shape of the light-shielding film pattern was observed, and as a result, the cross-sectional shape was vertical and was good.
於上述實施例1中，使遮光膜成膜後之加熱處理溫度為170℃，除此以外以與實施例1相同之方式，製作FPD用大型光罩毛胚、及FPD用大型光罩。藉由X射線繞射法測定FPD用大型光罩毛胚中之遮光膜之結晶性，可確認到CrN(200)之繞射峰值及Cr(110)之繞射峰值，且由CrN(200)之繞射峰值所算出之微晶尺寸為10 nm。另外，FPD用大型光罩之遮光膜圖案，於平面觀察圖案時圖案邊緣之凹凸(模糊)未滿0.1 μm，皆為良好。另外，FPD用大型光罩之面內之圖案線寬均勻性亦較良好。進而，觀察遮光膜圖案之剖面形狀，結果為剖面形狀垂直，為良好。In the above-mentioned Example 1, a large-sized photomask blank for FPD and a large-sized photomask for FPD were produced in the same manner as in Example 1 except that the heat treatment temperature after the formation of the light-shielding film was 170 °C. The crystallinity of the light-shielding film in the large-sized mask blank for FPD was measured by the X-ray diffraction method, and the diffraction peak of CrN (200) and the diffraction peak of Cr (110) were confirmed, and CrN (200) was confirmed. The crystallite size calculated from the diffraction peak is 10 nm. In addition, the FPD uses a light-shielding film pattern of a large photomask, and the unevenness (blur) of the edge of the pattern when the pattern is viewed in a plane is less than 0.1 μm. In addition, the pattern line width uniformity in the plane of the large mask of the FPD is also good. Further, the cross-sectional shape of the light-shielding film pattern was observed, and as a result, the cross-sectional shape was vertical and was good.
於大型玻璃基板(合成石英，厚度為10 mm，尺寸為850 mm×1200 mm)上使用大型連續式濺鍍裝置，使於膜表面上形成有抗反射膜之遮光膜成膜。成膜係指分別在連續配置於大型連續式濺鍍裝置內之各空間(濺鍍室)內配置Cr靶材後，首先，將Ar氣體及CO2 氣體作為濺鍍氣體使CrO膜連續成膜，進而將Ar氣體、O2 氣體及N2 氣體作為濺鍍氣體使CrON膜連續成膜，製作出FPD用大型光罩毛胚。遮光膜於超高壓水銀燈之波長的i線(365 nm)至g線(436 nm)下，作成光學濃度為3.5之膜厚。對形成有遮光膜之玻璃基板進行加熱處理。對該遮光膜，藉由拉賽福背向散射分析(RBS)測定深度方向上之氮比例，結果可確認，該遮光膜係自玻璃基板側將鉻(Cr)含量設為1時氮(N)含量未滿0.5之層與氮(N)含量為0.5以上之層的積層膜，且氮自遮光膜之表面側向玻璃基板側階段性減少。A large-scale continuous sputtering apparatus is used on a large glass substrate (synthetic quartz, thickness 10 mm, size 850 mm × 1200 mm) to form a light-shielding film having an anti-reflection film formed on the surface of the film. Film formation means that after the Cr target is placed in each space (sputtering chamber) continuously disposed in the large-scale continuous sputtering apparatus, first, the Ar gas and the CO 2 gas are used as a sputtering gas to continuously form a CrO film. Further, an Ar gas, an O 2 gas, and an N 2 gas were used as a sputtering gas to continuously form a CrON film, thereby producing a large-sized photomask blank for FPD. The light-shielding film was formed at an optical density of 3.5 at an i-line (365 nm) to a g-line (436 nm) of the wavelength of the ultrahigh pressure mercury lamp. The glass substrate on which the light shielding film is formed is subjected to heat treatment. In the light-shielding film, the nitrogen ratio in the depth direction was measured by the Raschel backscattering analysis (RBS), and it was confirmed that the light-shielding film was nitrogen (N) when the chromium (Cr) content was set to 1 from the glass substrate side. A laminated film having a layer having a content of less than 0.5 and a layer having a nitrogen (N) content of 0.5 or more, and nitrogen is gradually reduced from the surface side of the light-shielding film toward the glass substrate side.
另外，對該遮光膜藉由X射線繞射法測定結晶性。其結果為，所獲得之遮光膜實質上僅確認到CrN(200)之繞射峰值，且由CrN(200)之繞射峰值所算出之微晶尺寸為11 nm。Further, the light-shielding film was measured for crystallinity by an X-ray diffraction method. As a result, the obtained light-shielding film substantially only confirmed the diffraction peak of CrN (200), and the crystallite size calculated from the diffraction peak of CrN (200) was 11 nm.
繼而，以與上述實施例1相同之方式，製作出FPD用大型光罩。Then, in the same manner as in the above-described first embodiment, a large-sized photomask for FPD was produced.
使用掃描型電子顯微鏡(SEM)觀察形成於該FPD用大型光罩上之遮光膜圖案，就任意之遮光膜圖案而言，平面觀察圖案時圖案邊緣之凹凸(模糊)均遠超過0.1 μm。另外，FPD用大型光罩之面內之圖案線寬均勻性惡化，觀察遮光膜圖案之剖面形狀，結果為形成基板側之圖案寬度較小、表面側之圖案寬度較大的圖案形狀，圖案形狀亦惡化。The light-shielding film pattern formed on the large-sized photomask for FPD was observed using a scanning electron microscope (SEM), and in any of the light-shielding film patterns, the unevenness (blur) of the edge of the pattern when the pattern was viewed in a plane was far more than 0.1 μm. In addition, the pattern line width uniformity in the surface of the large-sized photomask of the FPD is deteriorated, and the cross-sectional shape of the light-shielding film pattern is observed. As a result, the pattern shape on the substrate side is small, and the pattern width on the surface side is large. Also worsened.
使用上述實施例1、2、比較例之FPD用大型光罩製作FPD元件，確認到顯示不均，使用實施例1、2之FPD用大型光罩所製作之FPD元件中不存在顯示不均；然而，使用比較例1之FPD用大型光罩所製作之FPD元件中，存在可認為由光罩之灰色調圖案部中之模糊引起之顯示不均。The FPD elements were produced using the large-sized photomasks of the FPDs of the first and second embodiments of the first and second embodiments, and the display unevenness was observed. The display of the FPD elements produced by using the large-sized FPD masks of the first and second embodiments did not show display unevenness; However, in the FPD element produced by using the large-sized photomask for FPD of Comparative Example 1, there is a display unevenness which is considered to be caused by blurring in the gray tone pattern portion of the photomask.
1．．．透光性基板1. . . Light transmissive substrate
2．．．遮光膜2. . . Sunscreen
3．．．光阻膜3. . . Photoresist film
3a．．．光阻圖案3a. . . Resistive pattern
10．．．光罩毛胚10. . . Photomask blank
20．．．光罩20. . . Mask
圖1係表示藉由本發明所獲得之光罩毛胚之一實施形態之剖面圖。BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing an embodiment of a reticle blank obtained by the present invention.
圖2(a)至圖2(e)係表示使用光罩毛胚製造光罩之步驟之剖面圖。2(a) to 2(e) are cross-sectional views showing a step of manufacturing a photomask using a reticle blank.
1．．．透光性基板1. . . Light transmissive substrate
2．．．遮光膜2. . . Sunscreen
3．．．光阻膜3. . . Photoresist film
3a．．．光阻圖案3a. . . Resistive pattern
10．．．光罩毛胚10. . . Photomask blank
20．．．光罩20. . . Mask
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| JP6301383B2 (en) * | 2015-03-27 | 2018-03-28 | Hoya株式会社 | Photomask blank, photomask manufacturing method using the same, and display device manufacturing method |
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| JP6855645B1 (en) * | 2019-06-27 | 2021-04-07 | Hoya株式会社 | Manufacturing method of thin film substrate, multilayer reflective coating substrate, reflective mask blank, reflective mask and semiconductor device |
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