WO2007099910A1 - Plaque-support de photomasque et photomasque, et leur procede de fabrication - Google Patents

Plaque-support de photomasque et photomasque, et leur procede de fabrication Download PDF

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Publication number
WO2007099910A1
WO2007099910A1 PCT/JP2007/053528 JP2007053528W WO2007099910A1 WO 2007099910 A1 WO2007099910 A1 WO 2007099910A1 JP 2007053528 W JP2007053528 W JP 2007053528W WO 2007099910 A1 WO2007099910 A1 WO 2007099910A1
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WO
WIPO (PCT)
Prior art keywords
shielding film
light
photomask blank
photomask
film
Prior art date
Application number
PCT/JP2007/053528
Other languages
English (en)
Japanese (ja)
Inventor
Takeyuki Yamada
Masaru Mitsui
Original Assignee
Hoya Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hoya Corporation filed Critical Hoya Corporation
Priority to JP2008502774A priority Critical patent/JP5412107B2/ja
Priority to KR1020107023098A priority patent/KR101248740B1/ko
Publication of WO2007099910A1 publication Critical patent/WO2007099910A1/fr

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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
    • G03F1/54—Absorbers, e.g. of opaque materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
    • G03F1/38—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
    • G03F1/68—Preparation processes not covered by groups G03F1/20 - G03F1/50
    • G03F1/80—Etching
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
    • H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
    • H01L21/0274—Photolithographic processes
    • H01L21/0276—Photolithographic processes using an anti-reflective coating
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/033—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers
    • H01L21/0332—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
    • 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

Definitions

  • the present invention relates to a photomask blank and a photomask in which the wet etching characteristics of a light shielding film are optimized for a wet etching process for forming a light shielding film pattern, and a manufacturing method thereof.
  • the present invention relates to a photomask blank for manufacturing an FPD device, and a photomask manufactured using the photomask blank.
  • a fine pattern is formed using a photolithography method.
  • a substrate called a photomask is usually used for forming this fine pattern.
  • This photomask is generally a light-transmitting glass substrate provided with a light-shielding fine pattern with a metal thin film and the like, and at least one photolithography method is used for manufacturing the photomask.
  • Photomask blanks having a light-shielding film on a light-transmitting substrate such as a glass substrate are used for manufacturing a photomask by a photolithography method.
  • a photomask using this photomask blank is manufactured by exposing the resist film formed on the photomask blank to a desired pattern exposure and developing the resist film in accordance with the desired pattern exposure.
  • a resist film formed on the photomask blank is subjected to a desired pattern exposure, and then a developing solution is supplied to dissolve a portion of the resist film that is soluble in the developing solution. Form. Further, in the above etching process, using this resist pattern as a mask, the resist pattern is formed by, for example, wet etching to dissolve a portion where the resist film is formed and the light shielding film is exposed, thereby making the desired mask pattern translucent. Form on the substrate. Thus, a photomask is completed.
  • Patent Document 1 describes a photomask blank provided with a chromium film containing chromium carbide as a light shielding film on a transparent substrate as a mask blank suitable for wet etching. It is. Patent Document 2 also has a laminated film of a halftone material film and a metal film on a transparent substrate as a mask blank that is also suitable for wet etching, and this metal film is formed from the surface side to the transparent substrate side. There is a region composed of materials with different etching rates, and for example, a halftone phase shift mask blank made of a CrNZCrC metal film and a CrON antireflection film is described.
  • photomasks used for manufacturing components such as color filters, TFT (thin film transistors) arrays and reflectors in liquid crystal display devices have a larger substrate size than LSI photomasks. . Therefore, compared with the case where the substrate size is small due to the large substrate size, the factors of the manufacturing principle limit (the limit surface derived from the manufacturing method and the manufacturing equipment) and the manufacturing condition fluctuation (process fluctuation) Therefore, variations in various characteristics (film composition, film quality, transmittance, reflectance, optical density, etching characteristics, other optical characteristics, film thickness, etc.) occur in-plane and between substrates. It has a feature that it is difficult to obtain a uniform characteristic between them. Such features tend to increase as the size and definition of FPD (Flat Panel Display) increases.
  • FPD Full Panel Display
  • the mask pattern formed over the entire surface of the large substrate is free from jaggedness and has a good cross-sectional shape.
  • the cross-sectional shape of the mask pattern formed on the photomask is substantially perpendicular to the film surface.
  • Patent Document 1 Japanese Patent Publication No. 62-32782
  • Patent Document 2 Japanese Patent No. 2983020
  • a photomask blank that is an original photomask used for manufacturing a liquid crystal display device
  • a light shielding film in which a chromium oxide (CrO) film and a chromium (Cr) film are laminated on a glass substrate is formed.
  • a light-shielding film formed by laminating a chromium oxide (CrO) film, a chromium (Cr) film, and a chromium oxide (CrO) film on a glass substrate.
  • the chromium oxide (CrO) film described above is an antireflection film having an antireflection function that reduces reflection of the film surface with respect to exposure light.
  • the photomask blank is formed by wet etching using the etchant of ceric ammonium nitrate, perchloric acid and pure water with the resist pattern formed on the light shielding film as a mask. A photomask was made.
  • the miniaturization of the mask pattern has advanced! / Under the circumstances! /
  • the mask pattern is not smooth (the pattern when the mask pattern is viewed in plan).
  • the edge roughness maximum distance between the concave and convex portions of the pattern edge)
  • the unevenness in the mask pattern and the cross-sectional shape of the pattern cause uneven display when a liquid crystal display device is manufactured using a photomask.
  • the present invention has been made to solve the conventional problems, and an object of the present invention is to optimize the wet etching characteristics of the light shielding film to thereby improve the cross-sectional shape of the light shielding film. It is another object of the present invention to provide a photomask blank and a photomask capable of forming a pattern, and further capable of forming a light-shielding film pattern with extremely small pattern irregularities, and a manufacturing method thereof.
  • the cross-sectional shape of the light-shielding film pattern formed by the wet etching process is favorable due to restrictions such as the film thickness of the light-shielding film and the composition gradient in the depth direction of the light-shielding film.
  • the present inventor has intensively studied and found that there is a correlation between the crystallinity of chromium constituting the chromium-based light-shielding film and the wet etching characteristics of the light-shielding film.
  • the present invention has the following configuration.
  • a photomask blank having a light-shielding film on a light-transmitting substrate the photomaster blank is patterned by wet etching using a mask pattern formed on the light-shielding film as a mask.
  • a photomask blank for wet etching processing corresponding to a photomask manufacturing method, wherein the light-shielding film also has a material force including chromium, and a diffraction peak force of CrN (200) by X-ray diffraction is also calculated.
  • Configuration 2 The photomask according to Configuration 1, wherein the light-shielding film is a film having diffraction peaks obtained by an X-ray diffraction method having a diffraction peak of CrN (200) and a diffraction peak of Cr (110). It is blank.
  • a photomask blank manufacturing method including a step of forming a light-shielding film containing chromium on a light-transmitting substrate by sputtering film formation using a target having a material strength containing chromium.
  • the photomask blank is a photomask blank for wet etching corresponding to a photomask manufacturing method in which the light shielding film is patterned by wet etching using a resist pattern formed on the light shielding film as a mask.
  • a method of manufacturing a photomask blank characterized by controlling the crystallinity of chromium constituting the light shielding film so that a cross-sectional shape of the light shielding film pattern formed by the wet etching process has a predetermined shape It is.
  • the structure 7 is characterized in that after forming the light shielding film, the crystallinity of chromium constituting the light shielding film is controlled by adjusting a heat treatment condition applied to the light shielding film. This is a method for producing a photomask blank.
  • (Configuration 12) A photomask manufacturing method comprising a step of patterning the light-shielding film in the photomask blank obtained by the manufacturing method according to any one of configurations 7 to 11 by a wet etching process It is.
  • the photomask blank of the present invention is a photomask blank having a light shielding film on a light-transmitting substrate, and the photomask blank is a mask pattern formed on the light shielding film.
  • a photomask blank for wet etching corresponding to a method for producing a photomask for patterning the light shielding film by wet etching using the mask as a mask, and the light shielding film also has a material force including chromium,
  • the diffraction peak force of CrN (200) by X-ray diffraction is calculated as a film whose crystallite size is lOnm or less.
  • the crystallinity of the light shielding film is calculated from the diffraction peak of CrN (200).
  • the pattern of the light shielding film can be made extremely small when the light shielding film is patterned by wet etching. It becomes possible, cross-sectional shape of the light shielding Makupa turn a good shape.
  • the crystallite size for calculating the diffraction peak force of CrN (200) is smaller! /, But the cross-sectional shape of the light-shielding film pattern is preferred. From the productivity such as film formation speed It is preferable that the size is too small.
  • the crystallite size calculated from the diffraction peak of CrN (200) is preferably 5 nm or more and lOnm or less.
  • the crystallinity of the light-shielding film is that the diffraction peak obtained by the X-ray diffraction method has a diffraction peak of CrN (200) and a diffraction peak of Cr (110). This is preferable because it makes it easier to control the shape of the light-shielding film pattern.
  • the light shielding film is a film containing nitrogen (N) in the entire region in the depth direction, so that the wet etching rate can be increased and the resist film formed on the light shielding film. Therefore, a finer and higher-definition light-shielding film pattern can be formed.
  • the light shielding film can form an antireflection layer containing oxygen in the upper layer portion thereof.
  • an antireflection layer By forming such an antireflection layer, the reflectance at the exposure wavelength can be suppressed to a low reflectance, so that multiple reflections with the projection exposure surface are suppressed when the mask pattern is transferred to the transfer target. In addition, it is possible to suppress a decrease in imaging characteristics.
  • the photomask blank is a large substrate, and a photomask blank for manufacturing an FPD device that requires dimensional accuracy of a light-shielding film pattern over the entire surface of the substrate. Suitable for!
  • the light-shielding film pattern formed by patterning the light-shielding film in the photomask blank according to any one of Configurations 1 to 5 by a wet etching process has a good cross-sectional shape.
  • the photomask is a good photomask with extremely small shading of the light shielding film pattern.
  • a photomask blank having a step of forming a light-shielding film containing chromium on a light-transmitting substrate by sputtering film formation using a target having a material strength containing chromium
  • the photomask blank is used for a wet etching process corresponding to a photomask manufacturing method for patterning the light shielding film by a wet etching process using a resist pattern formed on the light shielding film as a mask.
  • the crystallinity of chromium constituting the light-shielding film is adjusted so that the cross-sectional shape of the light-shielding film pattern formed by the wet etching process is a predetermined shape. Control.
  • the crystallinity of the light shielding film it is possible to control the wet etching characteristics of the light shielding film, which results in a favorable cross-sectional shape of the light shielding film pattern, and further the light shielding film pattern. It can be controlled so that the jaggedness becomes extremely small.
  • the crystallinity of chromium constituting the light shielding film is suitably controlled by adjusting the heat treatment conditions applied to the light shielding film. That's right.
  • the crystallinity of chromium is, for example, the crystallite size of CrN (200), and the heat treatment condition applied to the light shielding film is adjusted after the light shielding film is formed as in the structure 8. Therefore, it is preferable to control the crystallite size of chromium constituting the light shielding film.
  • the heat treatment for the light shielding film is a heat treatment before or after the formation of the resist film formed on the light shielding film.
  • a beta process for the purpose of improving the adhesion force, which is performed before the resist film is formed, or a pre-beta process after the resist film is formed it is preferable to control the crystallinity of chromium (for example, the crystallite size of chromium) constituting the light-shielding film by adjusting these heat treatment conditions.
  • the cross-sectional shape of the light-shielding film pattern formed by the wet etching process is substantially perpendicular to the film surface, as in Configuration 10. This is preferable because the cross-sectional shape of the light shielding film pattern can be well controlled.
  • the photomask blank is a large substrate, and a photomask blank for manufacturing an FPD device that requires dimensional accuracy of a light-shielding film pattern over the entire surface of the substrate. Suitable for!
  • a photomask manufacturing method comprising a step of patterning the light-shielding film in the photomask blank obtained by the manufacturing method according to any one of Configurations 7 to 11 by wet etching treatment
  • the light-shielding film pattern formed by performing the wet etching process has a good cross-sectional shape, and a good photomask with extremely small shading of the light-shielding film pattern can be obtained.
  • the wet etching characteristics of the light-shielding film are optimized and the light-shielding film is optimized by setting the crystallinity of the light-shielding film to a crystallite size for calculating the diffraction peak force of CrN (200). It is possible to provide a photomask blank in which the cross-sectional shape of the film pattern has a favorable shape, and further, the shading of the light-shielding film pattern can be extremely reduced.
  • FIG. 1 is a cross-sectional view showing an embodiment of a photomask blank obtained by the present invention.
  • FIG. 2 is a cross-sectional view showing a photomask manufacturing process using a photomask blank. Explanation of symbols
  • FIG. 1 is a cross-sectional view showing a first embodiment of a photomask blank according to the present invention.
  • a photomask blank 10 in FIG. 1 is in the form of a photomask blank for manufacturing an FPD having a light-shielding film 2 on a translucent substrate 1.
  • the photomask blank 10 is a resist pattern formed on the light shielding film 2. This is a mask blank for wet etching corresponding to a method for producing a photomask for patterning the light-shielding film 2 by wet etching.
  • the light-shielding film 2 is a light-shielding film containing chromium formed on the light-transmitting substrate 1 by a sputtering film using a target containing chromium.
  • a glass substrate is generally used as the translucent substrate 1. Since a glass substrate is excellent in flatness and smoothness, when pattern transfer onto a transfer substrate using a photomask is performed, highly accurate pattern transfer can be performed without causing distortion of the transfer pattern.
  • the light-shielding film 2 is configured so that the light-shielding film pattern formed by wet etching treatment has extremely small irregularities and has a predetermined cross-sectional shape.
  • the crystallinity of chrome is calculated so that the crystallite size calculated from the diffraction peak of CrN (200) is less than lOnm.
  • the crystallinity of chromium constituting the light shielding film 2 is expressed by a diffraction peak force CrN (200) obtained by an X-ray diffraction method.
  • the diffraction peak and Cr (l lO) diffraction peak are set.
  • the wet etching characteristics of the light-shielding film 2 can be controlled, whereby the light-shielding film pattern has a good cross-sectional shape and the light-shielding film pattern.
  • the jaggedness can be extremely small.
  • the crystallinity of 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.
  • the heat treatment for the light shielding film 2 is, for example, a heat treatment before or after the formation of the resist film formed on the light shielding film 2.
  • a beta process for the purpose of improving the adhesion force, which is performed before the resist film is formed, or a pre-beta process after the resist film is formed is preferable to control the crystallinity of chromium constituting the light-shielding film by adjusting these heat treatment conditions.
  • the crystallinity of the light-shielding film 2 is set to a crystal size of lOnm or less where the diffraction peak force of CrN (200) by X-ray diffraction is also calculated, and the diffraction peak obtained by the X-ray diffraction method is the diffraction peak of CrN (200) And a film having a diffraction peak of Cr (l lO)
  • a material containing chromium and nitrogen more preferably a material containing chromium, nitrogen, and carbon, more preferably a material containing chromium, nitrogen, carbon, and oxygen.
  • Heat treatment conditions are 80 ° C or higher. It can be obtained by heat treatment at a heating temperature of 180 ° C or lower, preferably 100 ° C or higher and 150 ° C or lower.
  • the cross-sectional shape of the light shielding film pattern formed by the wet etching process is desirably a shape that is substantially perpendicular to the film surface.
  • the wet etching characteristics of the light shielding film 2 can be controlled by controlling the crystallinity of the light shielding film 2.
  • the cross-sectional shape of the light-shielding film pattern becomes the above-mentioned favorable shape, and the light-shielding film pattern can be controlled to be extremely small, so that the present invention is suitable.
  • Specific examples of the material of the light shielding film 2 include a material containing chromium and nitrogen.
  • the content of chromium (Cr) contained in the light shielding film 2 is 1, the depth of the light shielding film 2 increases.
  • a region where the nitrogen (N) content is 0.5 or more and a region where the nitrogen (N) content is less than 0.5 are present.
  • the translucent substrate side force is such that when the chromium (Cr) content is 1, the nitrogen (N) content is less than 0.5 and the nitrogen (N) content is A layer of a layer that is 0.5 or more, a layer that has a nitrogen (N) content of 0.5 or more when the chromium (Cr) content is 1 from the translucent substrate side, and nitrogen ( (N) content of less than 0.5 and nitrogen (N) content strength of SO.5 or more of laminated films, and translucent substrate side chromium (Cr) content of 1 A layered film of a layer in which the nitrogen (N) content is 0.5 or more and a layer in which the nitrogen (N) content is less than 0.5 can be given.
  • the light shielding film is a laminated film
  • chromium (Cr) and nitrogen (N) contained in the light shielding film may change stepwise or may change continuously.
  • the light shielding film 2 may further contain an additive element such as oxygen, carbon, or fluorine.
  • the light-shielding film has a good cross-sectional shape with no mask pattern over the entire surface of a large substrate of 330 mm x 450 mm or more used for FPD manufacturing.
  • the material of the light-shielding film is a material containing chromium and nitrogen
  • the translucent substrate side force is nitrogen (N) when the chromium (Cr) content is 1. It is preferable to form a laminated film of a layer having a content of less than 0.5 and a layer having a nitrogen (N) content of 0.5 or more.
  • the method for forming the light shielding film 2 is not particularly limited, but a sputtering film forming method is particularly preferable. According to the sputtering film forming method, a uniform film having a constant film thickness can be formed, which is suitable for the present invention.
  • a chromium (Cr) target is used as the sputtering target, and the sputtering gas introduced into the chamber is argon gas or helium.
  • an inert gas such as lithium gas and a gas such as oxygen, nitrogen, carbon dioxide, or nitrogen monoxide.
  • a light-shielding film containing oxygen in chromium can be formed, and nitrogen gas is used as the inert gas such as argon gas.
  • nitrogen gas is used as the inert gas such as argon gas.
  • a light shielding film containing nitrogen can be formed on the chromium, and when a sputtering gas obtained by mixing nitrogen monoxide gas with an inert gas such as argon gas is used, chromium is added.
  • a light shielding film containing nitrogen and oxygen can be formed.
  • a sputtering gas in which methane gas is mixed with an inert gas such as argon gas is used, a light shielding film containing carbon in chromium can be formed.
  • the film thickness of the light shielding film 2 is set so that the optical density with respect to the exposure light is, for example, 3.0 or more.
  • the thickness of the light shielding film 2 is preferably 200 nm or less. If the film thickness exceeds 200 nm, the film thickness variation in the substrate surface of the light shielding film 2 tends to increase, and the pattern accuracy of the light shielding film pattern deteriorates, which is not preferable. Incidentally, the lower limit of the thickness of the light shielding film 2 can be reduced as long as a desired optical density is obtained.
  • the light shielding film 2 is not limited to a multilayer such as a laminated film as described above, and may be a single layer.
  • the surface layer portion (upper layer portion) may have an antireflection function.
  • the antireflection layer having an antireflection function for example, materials such as CrO, CrCO, CrNO, CrCON are preferably mentioned.
  • the antireflection layer may also be provided on the translucent substrate side as necessary.
  • the light shielding film 2 is different in content of chromium and elements such as oxygen, nitrogen, and carbon in the depth direction, and is stepwise in the antireflection layer of the surface layer portion and the other layers (light shielding layers).
  • a composition gradient film having a composition gradient continuously may be used.
  • a method of appropriately switching the type (composition) of the sputtering gas during the above-described sputtering film formation during the film formation is suitable.
  • the photomask blank may have a form in which a resist film 3 is formed on the light shielding film 2 as shown in FIG.
  • the film thickness of the resist film 3 is preferably as thin as possible in order to improve the pattern accuracy (CD accuracy) of the light shielding film.
  • the lower limit of the thickness of the resist film is set so that the resist film remains when the light shielding film 2 is wet etched using the resist pattern as a mask.
  • the method of manufacturing a photomask using the photomask blank 0 includes a step of patterning the light shielding film 2 of the photomask blank 10 using wet etching. A step of performing desired pattern exposure (pattern drawing) on the resist film formed on the substrate, a step of developing the resist film in accordance with the desired pattern exposure to form a resist pattern, and the light shielding film along the resist pattern. And a step of peeling and removing the remaining resist pattern.
  • FIG. 2 is a cross-sectional view sequentially showing photomask manufacturing processes using the photomask blank 10.
  • FIG. 2 (a) shows a state in which a resist film 3 is formed on the light shielding film 2 of the photomask blank 10 of FIG.
  • the resist material either a positive resist material or a negative resist material can be used.
  • FIG. 2B shows a step of performing desired pattern exposure (pattern drawing) on the resist film 3 formed on the photomask blank 10. Note that turn exposure is performed using a laser lithography system. As the above-described resist material, those having photosensitivity corresponding to laser are used.
  • FIG. 2 (c) shows the resist pattern developed by developing the resist film 3 according to the desired pattern exposure.
  • the process of forming the screen 3a is shown.
  • the resist film 3 formed on the photomask blank 10 is exposed to a desired pattern, and then a developer is supplied to dissolve a portion of the resist film that is soluble in the developer. Form.
  • an aqueous solution obtained by adding perchloric acid to ceric nitrate is generally used.
  • the wet etching conditions such as the concentration, temperature, and processing time of the etching solution are appropriately set such as the pattern cross-sectional characteristics of the light shielding film.
  • FIG. 2 (e) shows a photomask 20 obtained by peeling off and removing the remaining resist pattern 3a.
  • the photomask blank is not limited to a so-called binary mask photomask blank in which a light-shielding film is formed on a light-transmitting substrate, but a light-shielding portion that shields exposure light, a light-transmitting portion that transmits exposure light,
  • a photomask blank for a gray tone mask having a gray tone portion which is a light transmitting region may be used.
  • the gray tone portion may be a semi-transparent film whose material is selected so as to have a desired transmittance with respect to exposure light, or the same material as the light-shielding film, and the resolution limit of exposure light may be The following fine light-shielding film pattern may be used.
  • a single tone mask with a semi-transparent film pattern is a semi-transparent film-type gray-tone mask in which a semi-transparent film pattern is formed under a light-shielding film pattern.
  • a gray-tone mask of a semi-transparent film placed type in which the film pattern is formed on the light shielding film pattern may be used.
  • the translucent substrate generally includes a glass substrate, and includes a synthetic quartz glass substrate, a soda lime glass substrate, an alkali-free glass substrate, and the like.
  • a light-transmitting substrate for manufacturing an FPD device for example, a large-sized substrate of 330 mm X 45 Omm to 1400 mm X 1600 mm is meant.
  • the photomask blank and photomask for manufacturing the FPD device include mask blanks for manufacturing FPD devices such as LCD (liquid crystal display), plasma display, and organic EL (electroluminescence) display. And a photomask.
  • the LCD manufacturing mask includes all photomasks necessary for LCD manufacturing.
  • TFT thin film transistor
  • TFT channel part and contact hole part low-temperature polysilicon TFT
  • color filter color filter
  • a photomask for forming a reflector or the like is included.
  • Other display device manufacturing masks include all photomasks required for the manufacture of organic EL (electral luminescence) displays, plasma displays, and the like.
  • a large in-line sputtering device on a large glass substrate (synthetic quartz 10mm thick, size 850mmX 1200mm), a light-shielding film with an antireflection film formed on the film surface was formed.
  • Cr targets are placed in each space (sputtering chamber) arranged continuously in a large in-line sputtering system, and Ar gas and N gas are sputtered first.
  • CrN film as gas
  • CrC film as Ar gas and CH gas as sputtering gas
  • a CrON film was continuously formed using Ar gas and NO gas as sputtering gases to produce a large photomask blank for FPD.
  • the light-shielding film was formed to have an optical density of 3.5 from the i-line (365 nm) to the g-line (436 nm), which is the wavelength of the ultra-high 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.
  • nitrogen (N) was obtained when the content of chromium (Cr) on the side of the glass substrate was 1.
  • ⁇ Bragg angle (diffraction angle 2 ⁇ 1Z2).
  • a large photomask for FPD that has a normal pattern of 5 ⁇ m width and a gray-tone pattern of 1 ⁇ m width (a fine light-shielding pattern that is less than the resolution limit of a large FPD exposure machine and a pattern that consists of a fine transmission part) was made.
  • Example 1 a large photomask blank for FPD and a large photomask for FPD were produced in the same manner as in Example 1 except that the heat treatment temperature after forming the light shielding film was set to 170 ° C.
  • the crystallinity of the light-shielding film in a large photomask blank for FPD was measured by X-ray diffraction, a CrN (200) diffraction peak and a Cr (110) diffraction peak were confirmed, and Cr N (200) diffraction was confirmed.
  • the crystallite size calculated from the peak was 10 nm.
  • the unevenness (jaggedness) of the pattern edge when the pattern was viewed in plan was good at less than 0.1 ⁇ m.
  • large photomass for FPD The pattern line width uniformity in the surface of the pattern was also good. Furthermore, when the cross-sectional shape of the pattern of the light shielding film was observed, the cross-sectional shape was vertical and good.
  • a large in-line sputtering device on a large glass substrate (synthetic quartz 10mm thick, size 850mmX 1200mm), a light-shielding film with an antireflection film formed on the film surface was formed.
  • Cr targets are placed in each space (sputtering chamber) arranged continuously in a large in-line sputtering system, and Ar gas and CO gas are sputtered first.
  • a large photomask blank for FPD was fabricated by continuously forming an ON film.
  • the light-shielding film was formed to have an optical density of 3.5 from the i-line (365 nm) to the g-line (436 nm), which is the wavelength of the ultra-high pressure mercury lamp.
  • the glass substrate with the light-shielding film was subjected to heat treatment.
  • the ratio of nitrogen in the depth direction of this light-shielding film was measured by Rutherford backscattering analysis (RBS).
  • the nitrogen (N) content was A layered film of less than 0.5 layer and a layer in which the content of nitrogen (N) is 0.5 or more. Nitrogen is gradually reduced as the surface side force of the light shielding film is also directed toward the glass substrate side. It was confirmed that the film was sizzling!
  • An FPD device was fabricated using the large FPD photomasks of Examples 1 and 2 and Comparative Example above, and the display unevenness was confirmed.
  • the large FPD photomask of Example 2 Although the manufactured FPD device has a strong display unevenness, the FPD device manufactured using the large FPD photomask of Comparative Example 1 has a display unevenness that seems to be caused by the jaggedness in the gray-tone pattern part of the photomask. It was confirmed that there is.

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  • Physics & Mathematics (AREA)
  • 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)

Abstract

La présente invention concerne une plaque-support de photomasque et un photomasque, qui peuvent former un motif d'un film d'ombrage ayant une excellente forme de coupe par optimisation des caractéristiques de gravure humide du film, et qui peuvent former un motif d'un film d'ombrage ayant des irrégularités très petites. La plaque-support de photomasque comprenant le film d'ombrage sur un substrat transparent est soumise à un traitement de gravure humide qui copie un masque par un motif de masque formé sur le film d'ombrage. Ce traitement de gravure humide correspond à un procédé de fabrication de photomasque pour la modélisation du film d'ombrage. Ce film d'ombrage se compose d'un matériau contenant du chrome et présente une taille de cristal inférieure ou égale à 10 nm, telle que calculée à partir d'un pic de diffraction de CrN(200) par une diffraction des rayons X. Le film d'ombrage est modélisé par le traitement de gravure humide pour produire un photomasque doté du motif de film d'ombrage sur le substrat.
PCT/JP2007/053528 2006-02-28 2007-02-26 Plaque-support de photomasque et photomasque, et leur procede de fabrication WO2007099910A1 (fr)

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JP2008502774A JP5412107B2 (ja) 2006-02-28 2007-02-26 フォトマスクブランクの製造方法、及びフォトマスクの製造方法
KR1020107023098A KR101248740B1 (ko) 2006-02-28 2007-02-26 포토마스크 블랭크 및 포토마스크와 그들의 제조 방법

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JP2008203373A (ja) * 2007-02-16 2008-09-04 Clean Surface Gijutsu:Kk ハーフトーンブランクス及びハーフトーンブランクスの製造方法
JP2016105158A (ja) * 2014-11-20 2016-06-09 Hoya株式会社 フォトマスクブランク及びそれを用いたフォトマスクの製造方法、並びに表示装置の製造方法
JP2019117376A (ja) * 2017-12-26 2019-07-18 Hoya株式会社 フォトマスクブランクおよびフォトマスクの製造方法、並びに表示装置の製造方法
WO2020261986A1 (fr) * 2019-06-27 2020-12-30 Hoya株式会社 Substrat fixé à un film mince, substrat fixé à un film réfléchissant multicouche, ébauche de masque réfléchissant, masque réfléchissant, et procédé de fabrication de dispositif à semi-conducteur
JP2021089422A (ja) * 2019-11-26 2021-06-10 Hoya株式会社 マスクブランク、転写用マスク、及び半導体デバイスの製造方法
TWI838542B (zh) 2019-06-27 2024-04-11 日商Ｈｏｙａ股份有限公司 附薄膜之基板、附多層反射膜之基板、反射型光罩基底、反射型光罩及半導體裝置之製造方法

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KR100390007B1 (ko) * 2002-02-05 2003-07-04 주식회사 엔비자인 미네랄이 보존되는 나노여과 정수방법
JP6301383B2 (ja) * 2015-03-27 2018-03-28 Hoya株式会社 フォトマスクブランク及びこれを用いたフォトマスクの製造方法、並びに表示装置の製造方法
JP6540278B2 (ja) * 2015-06-29 2019-07-10 大日本印刷株式会社 光学素子の製造方法
KR102444967B1 (ko) * 2021-04-29 2022-09-16 에스케이씨솔믹스 주식회사 블랭크 마스크 및 이를 이용한 포토마스크

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JPH02212841A (ja) * 1989-02-14 1990-08-24 Toppan Printing Co Ltd フオトマスクおよびフオトマスクブランク
JPH05297570A (ja) * 1992-04-20 1993-11-12 Toppan Printing Co Ltd フォトマスクブランクの製造方法
JPH07118829A (ja) * 1993-10-19 1995-05-09 Nissin Electric Co Ltd 窒化クロム膜被覆基体及びその製造方法
JPH10163105A (ja) * 1996-11-23 1998-06-19 Lg Semicon Co Ltd Ｘ線マスクの吸収体及びその製造方法
JPH11172426A (ja) * 1997-12-05 1999-06-29 Ulvac Corp 薄膜の結晶配向性制御成膜法
JP3276954B2 (ja) * 1998-07-31 2002-04-22 ホーヤ株式会社 フォトマスクブランク、フォトマスク、及びそれらの製造方法並びに微細パターン形成方法

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008203373A (ja) * 2007-02-16 2008-09-04 Clean Surface Gijutsu:Kk ハーフトーンブランクス及びハーフトーンブランクスの製造方法
JP2016105158A (ja) * 2014-11-20 2016-06-09 Hoya株式会社 フォトマスクブランク及びそれを用いたフォトマスクの製造方法、並びに表示装置の製造方法
JP2019117376A (ja) * 2017-12-26 2019-07-18 Hoya株式会社 フォトマスクブランクおよびフォトマスクの製造方法、並びに表示装置の製造方法
JP7113724B2 (ja) 2017-12-26 2022-08-05 Hoya株式会社 フォトマスクブランクおよびフォトマスクの製造方法、並びに表示装置の製造方法
WO2020261986A1 (fr) * 2019-06-27 2020-12-30 Hoya株式会社 Substrat fixé à un film mince, substrat fixé à un film réfléchissant multicouche, ébauche de masque réfléchissant, masque réfléchissant, et procédé de fabrication de dispositif à semi-conducteur
JP6855645B1 (ja) * 2019-06-27 2021-04-07 Hoya株式会社 薄膜付基板、多層反射膜付基板、反射型マスクブランク、反射型マスク及び半導体装置の製造方法
TWI838542B (zh) 2019-06-27 2024-04-11 日商Ｈｏｙａ股份有限公司 附薄膜之基板、附多層反射膜之基板、反射型光罩基底、反射型光罩及半導體裝置之製造方法
JP2021089422A (ja) * 2019-11-26 2021-06-10 Hoya株式会社 マスクブランク、転写用マスク、及び半導体デバイスの製造方法
JP7154626B2 (ja) 2019-11-26 2022-10-18 Hoya株式会社 マスクブランク、転写用マスク、及び半導体デバイスの製造方法

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JPWO2007099910A1 (ja) 2009-07-16
KR20080106307A (ko) 2008-12-04
KR20100124333A (ko) 2010-11-26
TW200739247A (en) 2007-10-16
KR101071471B1 (ko) 2011-10-10
KR101248740B1 (ko) 2013-03-28
JP5412107B2 (ja) 2014-02-12

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