CN115903365A - Photomask blank, photomask, method for manufacturing photomask, and method for manufacturing display device - Google Patents

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

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Publication number
CN115903365A
CN115903365A CN202211150078.2A CN202211150078A CN115903365A CN 115903365 A CN115903365 A CN 115903365A CN 202211150078 A CN202211150078 A CN 202211150078A CN 115903365 A CN115903365 A CN 115903365A
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CN
China
Prior art keywords
light
photomask
shielding film
film
shielding
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Pending
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CN202211150078.2A
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Chinese (zh)
Inventor
田边胜
浅川敬司
中村仁美
安森顺一
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Hoya Corp
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Hoya Corp
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Publication date
Priority claimed from JP2022131956A external-priority patent/JP2023051759A/en
Application filed by Hoya Corp filed Critical Hoya Corp
Publication of CN115903365A publication Critical patent/CN115903365A/en
Pending legal-status Critical Current

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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
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/1303—Apparatus specially adapted to the manufacture of LCDs
    • 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

Abstract

[ problem ] to provide a photomask blank, a photomask, a method for manufacturing a photomask, and a method for manufacturing a display device, which have high antistatic breakdown characteristics and can reduce the load effect and the like compared to the conventional photomask blank. [ solution ] A photomask blank for manufacturing an FPD, for example, is characterized by comprising a transparent substrate and a light-shielding film on the transparent substrate, wherein the light-shielding film contains titanium (Ti) and silicon (Si), and the light-shielding film has a sheet resistance value of 40 Ω/sq or more. Thus, the antistatic breakdown property can be improved as compared with the conventional photomask blank, and the load effect can be reduced.

Description

Photomask blank, photomask, method for manufacturing photomask, and method for manufacturing display device
Technical Field
The present invention relates to a photomask blank for manufacturing a display device, a photomask, a method for manufacturing a photomask, and a method for manufacturing a display device.
Background
In recent years, in Display devices such as FPDs (Flat Panel displays) represented by LCDs (Liquid Crystal displays), high definition and high speed Display have been rapidly advanced with the screen size and wide viewing angle. Therefore, a photomask used in an exposure process in the manufacture of an FPD includes a binary mask, a phase shift mask, or the like in which a fine and highly precise transfer pattern is formed on a large-sized transparent substrate.
The photomask blank is a master of a photomask. The photomask includes, for example, a transparent substrate and a light shielding film pattern formed by patterning a light shielding film on the transparent substrate by wet etching.
In a photomask used for manufacturing such an FPD, static electricity is applied to the photomask in an exposure process, a transfer process, or the like, and electrostatic breakdown may partially occur in a transfer pattern. In particular, in a highly precise photomask with a finer pattern, electrostatic breakdown may occur between the finer patterns, and thus the photomask and the photomask blank are required to have high antistatic breakdown characteristics.
For example, patent document 1 describes forming a light-shielding film from a MoSi material, a TaSi material, a ZrSi material, or the like instead of a Cr material.
For example, patent document 2 discloses that the sheet resistance value of the light-shielding film is 10 Ω/sq or less.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open No. 2020-140106
Patent document 2: japanese patent laid-open publication No. 2019-168558
Disclosure of Invention
Problems to be solved by the invention
As described above, in a photomask used in the manufacture of an FPD, in order to suppress or avoid electrostatic breakdown between patterns, higher antistatic breakdown characteristics are required.
In addition, in etching of an optical film including a light-shielding film as part of a photomask manufacturing process, a loading effect in which an etching rate is different between a region with a high pattern density and a sparse region may occur. In recent FPD manufacturing with high definition (for example, 1000ppi or more), there is a demand for a photomask having a transfer pattern with an aperture of 6 μm or less, a line width of 4 μm or less, and specifically a diameter or width of 1.5 μm or less, in order to transfer a pattern with high resolution. In this case, it is also useful to reduce the load effect in order to form a fine pattern with high accuracy.
The present invention has been made to solve the above problems. That is, an object of the present invention is to provide a photomask blank, a photomask, a method for manufacturing a photomask, and a method for manufacturing a display device, which have high antistatic breakdown characteristics and can reduce a load effect and the like compared to the conventional photomask blank.
Means for solving the problems
In order to solve the above problem, the present invention has the following configuration.
(constitution 1)
Configuration 1 of the present invention is a photomask blank including a transparent substrate and a light-shielding film provided on the transparent substrate, wherein the light-shielding film contains titanium (Ti) and silicon (Si), and the light-shielding film has a sheet resistance value of 40 Ω/sq or more.
(constitution 2)
Constitution 2 of the present invention is the photomask blank according to constitution 1, characterized in that the light-shielding film has a sheet resistance value of 90 Ω/sq or less.
(constitution 3)
The constitution 3 of the present invention is: the photomask blank according to configuration 1, wherein the light-shielding film comprises a light-shielding layer made of a titanium silicide material containing titanium (Ti) and silicon (Si), and the light-shielding layer has a sheet resistance value of 40 Ω/sq or more.
(constitution 4)
The constitution 4 of the present invention is: the photomask blank according to constitution 3, characterized in that the light-shielding layer has a sheet resistance value of 90 Ω/sq or less.
(constitution 5)
The constitution 5 of the present invention is: as described in any one of configurations 1 to 4, the light-shielding film includes a light-shielding layer made of a titanium silicide material containing titanium (Ti) and silicon (Si), and the light-shielding layer further contains nitrogen (N) or oxygen (O).
(constitution 6)
The constitution 6 of the present invention is: the photomask blank according to any one of configurations 1 to 5, wherein the light-shielding film comprises a light-shielding layer made of a titanium silicide material containing titanium (Ti) and silicon (Si), and the light-shielding layer has a surface anti-reflection layer thereon.
(constitution 7)
The constitution 7 of the present invention is: the photomask blank according to configuration 6, wherein the surface anti-reflection layer is made of a titanium silicide-based material containing titanium (Ti) and silicon (Si), and contains nitrogen (N) or oxygen (O).
(constitution 8)
The constitution 8 of the present invention is: the photomask blank according to any one of configurations 1 to 7, wherein the light-shielding film comprises a light-shielding layer made of a titanium silicide material containing titanium (Ti) and silicon (Si), and a back-surface antireflection layer is provided between the transparent substrate and the light-shielding layer.
(constitution 9)
The constitution 9 of the present invention is: the photomask blank according to constitution 8, wherein the back surface antireflection layer is made of a titanium silicide-based material containing titanium (Ti) and silicon (Si), and contains nitrogen (N) or oxygen (O).
(constitution 10)
The constitution 10 of the present invention is: the photomask blank according to any one of configurations 1 to 9, wherein the light-shielding film has an etching mask film having an etching selectivity different from that of the light-shielding film.
(constitution 11)
The constitution 11 of the present invention is: the photomask blank according to constitution 10, wherein the etching mask film contains chromium (Cr).
(constitution 12)
The constitution 12 of the present invention is: the photomask blank according to constitution 11, characterized in that the etching mask film further contains nitrogen (N) or oxygen (O).
(constitution 13)
The present invention is a photomask having a transparent substrate and a light-shielding film provided on the transparent substrate and having a transfer pattern, wherein the light-shielding film contains titanium (Ti) and silicon (Si), and the light-shielding film has a sheet resistance value of 40 Ω/sq or more.
(constitution 14)
The constitution 14 of the present invention is: the photomask according to structure 13, wherein the light-shielding film has a sheet resistance value of 90 Ω/sq or less.
(constitution 15)
The constitution 15 of the present invention is: the photomask according to claim 13, wherein the light-shielding film comprises a light-shielding layer made of a titanium silicide material containing titanium (Ti) and silicon (Si), and the light-shielding layer has a sheet resistance value of 40 Ω/sq or more.
(constitution 16)
The constitution 16 of the present invention is: the photomask according to claim 15, wherein the light-shielding layer has a sheet resistance value of 90 Ω/sq or less.
(constitution 17)
The constitution 17 of the present invention is: the photomask according to claim 13, wherein the light-shielding film comprises a light-shielding layer made of a titanium silicide material containing titanium (Ti) and silicon (Si), and the light-shielding layer further contains nitrogen (N) or oxygen (O).
(constitution 18)
The constitution 18 of the present invention is: the photomask according to claim 13, wherein the light-shielding film comprises a light-shielding layer made of a titanium silicide material containing titanium (Ti) and silicon (Si), and the light-shielding layer has a surface anti-reflection layer thereon.
(constitution 19)
The constitution 19 of the present invention is: the photomask according to claim 18, wherein the surface antireflection layer is made of a titanium silicide-based material containing titanium (Ti) and silicon (Si), and contains nitrogen (N) or oxygen (O).
(constitution 20)
The constitution 20 of the present invention is: the photomask according to any one of configurations 13 to 19, wherein the light-shielding film includes a light-shielding layer made of a titanium silicide-based material containing titanium (Ti) and silicon (Si), and a back-surface antireflection layer is provided between the transparent substrate and the light-shielding layer.
(constitution 21)
The constitution 21 of the present invention is: the photomask according to claim 20, wherein the back surface antireflection layer is made of a titanium silicide-based material containing titanium (Ti) and silicon (Si), and contains nitrogen (N) or oxygen (O).
(constitution 22)
The present invention is a method for manufacturing a photomask, including the steps of: preparing a photomask blank constituting any one of 1 to 9; and a step of forming a transfer pattern on the transparent substrate by wet etching the light-shielding film using a resist pattern provided on the light-shielding film as a mask.
(constitution 23)
The present invention is a method for manufacturing a photomask, including the steps of: preparing a photomask blank constituting any one of 10 to 12; a step of performing wet etching on the etching mask film using a resist film pattern provided on the etching mask film as a mask to form an etching mask film pattern on the light-shielding film; and forming a transfer pattern on the transparent substrate by wet etching the light-shielding film using the etching mask film pattern as a mask.
(constitution 24)
The present invention in configuration 24 is a method for manufacturing a display device, including the steps of: the photomask obtained by the method for manufacturing a photomask according to configuration 22 or 23 is placed on a mask stage of an exposure apparatus, and the transfer pattern formed on the photomask is exposed and transferred to a resist formed on a substrate for a display apparatus.
(constitution 25)
The present invention is a method for manufacturing a display device, including the steps of: the photomask according to structure 13 is placed on a mask stage of an exposure apparatus, and the transfer pattern formed on the photomask is exposed and transferred to a resist formed on a substrate for a display device.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, for example, in a photomask blank and a photomask for manufacturing an FPD, the antistatic breakdown property can be improved compared to the conventional one. In addition, according to the present invention, since the load effect can be reduced, a highly precise photomask can be stably manufactured.
Drawings
Fig. 1 is a schematic cross-sectional view showing a film structure of a photomask blank according to embodiment 1 of the present invention.
Fig. 2 is a schematic cross-sectional view showing a film structure of a photomask blank according to embodiment 2 of the present invention.
Fig. 3 is a schematic cross-sectional view of a photomask blank according to embodiment 1 of the present invention, and is a cross-sectional view showing the layer structure of the light-shielding film in particular in detail.
Fig. 4A is a schematic cross-sectional view illustrating a process of manufacturing a photomask from the photomask blank of embodiment 1 of the present invention.
Fig. 4B is a schematic cross-sectional view further illustrating a process of manufacturing a photomask from the photomask blank of embodiment 1.
Fig. 4C is a schematic cross-sectional view further illustrating a process of manufacturing a photomask from the photomask blank of embodiment 1.
Fig. 4D is a schematic cross-sectional view further illustrating a process of manufacturing a photomask from the photomask blank of embodiment 1.
Fig. 5A is a schematic cross-sectional view showing a process of manufacturing a photomask from the photomask blank of embodiment 2 of the present invention.
Fig. 5B is a schematic cross-sectional view further illustrating a process of manufacturing a photomask from the photomask blank of embodiment 2.
Fig. 5C is a schematic cross-sectional view further illustrating a process of manufacturing a photomask from the photomask blank of embodiment 2.
Fig. 6 shows a schematic top view of a light shielding film pattern used for measuring the degree of the load effect in the embodiment of the present invention.
Detailed Description
Embodiments of the present invention will be specifically described below with reference to the drawings. The following embodiments are embodiments of the present invention, and the present invention is not limited to the embodiments. The photomask blank 10 corresponds to a master of a photomask 100 (fig. 4D and 5C) used for manufacturing a Display device such as an FPD (Flat Panel Display) typified by an LCD (Liquid Crystal Display) through a photolithography process.
Fig. 1 is a schematic longitudinal sectional view showing a film structure of a photomask blank 10 according to embodiment 1 of the present invention. The photomask blank 10 of embodiment 1 includes: a transparent substrate 20; a light shielding film 30 as a thin film for pattern formation formed on the transparent substrate 20; and an etching mask film 40 formed on the light-shielding film 30.
Fig. 2 is a schematic diagram showing a film configuration of photomask blank 10 according to embodiment 2 of the present invention. The photomask blank 10 according to embodiment 2 includes: a transparent substrate 20; and a light shielding film 30 formed on the transparent substrate 20.
< transparent substrate 20>
The transparent substrate 20 is transparent to the exposure light. The transparent substrate 20 has a transmittance of 85% or more, preferably 90% or more, with respect to the exposure light, assuming that there is no surface reflection loss. The transparent substrate 20 is formed of a material containing silicon (Si) and oxygen (O), and may be formed of synthetic quartz glass, aluminosilicate glass, soda-lime glass, and low thermal expansion glass (SiO) 2 -TiO 2 Glass, etc.). The transparent substrate 20 used in the display device application is generally a rectangular substrate. Specifically, the short side length of the main surface (the surface on which the light shielding film 30 is formed) of the transparent substrate 20 can be usedA transparent substrate 20 having a thickness of 300mm or more. In the photomask blanks 10 according to embodiments 1 and 2, the large-sized transparent substrate 20 having a main surface with a short side length of 300mm or more may be used.
< light-shielding film 30>
The light-shielding film 30 as the thin film for pattern formation may have a single-layer structure composed of only the light-shielding layer 31. The light-shielding film 30 may have a multilayer structure including the light-shielding layer 31 and the front anti-reflection layer 32 and/or the back anti-reflection layer 33. Here, fig. 3 is a vertical sectional view schematically showing, as an example, a photomask blank 10 in which the light-shielding film 30 is composed of 3 layers of a light-shielding layer 31, a front anti-reflection layer 32, and a back anti-reflection layer 33. According to the example of fig. 3, the front anti-reflection layer 32 is provided on the upper surface (the surface opposite to the side having the transparent substrate 20) of the light-shielding layer 31, and the back anti-reflection layer 33 is provided between the transparent substrate 20 and the light-shielding layer 31.
The light shielding film 30 may be formed of a titanium silicide-based material containing titanium (Ti) and silicon (Si). In general, as patterns become fine, it is useful to consider a loading effect that causes a difference in etching rate between a region where the pattern density is high and a sparse region. According to the study of the present inventors, it was confirmed that: by using a titanium silicide-based material for the light-shielding film 30, the loading effect is reduced as compared with a chromium-based compound and other metal silicide-based materials commonly used in photomask blanks for manufacturing display devices. The other metal silicide-based material is, for example, moSi (molybdenum silicide) -based material or ZrSi (zirconium silicide) -based material.
Further, according to photomask blanks 10 of embodiments 1 and 2, the edge cross-sectional shape of the light-shielding film pattern (transfer pattern) formed by wet etching of the light-shielding film 30 can be made substantially perpendicular to the main surface of the transparent substrate 20. In particular, in embodiments 1 and 2, a material that is homogeneous and has no composition gradient can be used to realize a well-patterned edge cross-sectional shape. Therefore, the pattern accuracy and the accuracy of ensuring the panel quality are improved, and the process control at the time of forming the light shielding film 30 is facilitated.
The atomic ratio of titanium (Ti) to silicon (Si) in the light shielding layer 31 is preferably 1:1.4 to 1: 3.4. If the proportion of titanium is too small, it is difficult to ensure sufficient light-shielding properties. From the viewpoint of chemical resistance and light resistance, the upper limit of the proportion of titanium is preferably as described above.
The light-shielding layer 31 constituting the light-shielding film 30 may further contain nitrogen (N) or oxygen (O). By containing these elements in the light-shielding film 30, the etching rate with respect to the wet etchant can be controlled, and the edge shape of the pattern cross section can be improved.
Specifically, the content of nitrogen (N) in the light-shielding layer 31 is preferably 0 to 10 atomic%. The content of oxygen (O) is preferably 0 to 5 atomic%. The light-shielding layer 31 may not contain nitrogen (N) or oxygen (O).
The front anti-reflection layer 32 and the back anti-reflection layer 33 are made of a titanium silicide material containing titanium (Ti) and silicon (Si), and may further contain nitrogen (N) or oxygen (O). By containing these elements, the reflectance with respect to exposure light or drawing light (light used in drawing on a resist film in manufacturing a photomask) can be reduced. The content of nitrogen (N) in the front anti-reflection layer 32 and the back anti-reflection layer 33 is preferably 10 atomic% to 55 atomic%. The content of oxygen (O) is preferably 0 to 10 atomic%. The front anti-reflection layer 32 and the back anti-reflection layer 33 may not contain oxygen (O).
In addition, in the photomask blanks 10 of embodiments 1 and 2, the sheet resistance value of the light-shielding film 30 is preferably 40 Ω/sq or more, and more preferably 42 Ω/sq or more, in order to improve the antistatic breakdown property. The sheet resistance value can be increased, for example, by increasing the amount of nitrogen (N) or silicon (Si) contained in the light-shielding film 30. On the other hand, if the content of nitrogen (N) or silicon (Si) is increased, the light-shielding property is degraded (in other words, the transmittance is improved). In addition, when the content of silicon is large, the etching selectivity with the transparent substrate becomes small. Thus, the sheet resistance value of the light-shielding film 30 is preferably set to 90 Ω/sq or less. When the light-shielding film 30 has a single-layer structure including only the light-shielding layer 31, the sheet resistance value of the light-shielding layer 31 is preferably 40 Ω/sq or more, and more preferably 90 Ω/sq or less for the same purpose.
The film thicknesses of the front anti-reflection layer 32 and the back anti-reflection layer 33 are much smaller than the film thickness of the light-shielding layer 31. Therefore, the sheet resistance values of the front anti-reflection layer 32 and the back anti-reflection layer 33 are negligibly small. Therefore, even when the light-shielding film 30 includes the front anti-reflection layer 32 and/or the back anti-reflection layer 33, the sheet resistance value of the light-shielding film 30 can be said to be substantially the same as the sheet resistance value of the light-shielding layer 31. Further, since the surface antireflection layer 32 is very thin, when a probe for measuring a sheet resistance value is brought into contact with the light-shielding film 30 of the photomask blank 10, the probe penetrates the surface antireflection layer 32 and comes into contact with the light-shielding layer 31. Therefore, even when the front anti-reflection layer 32 is formed on the light-shielding layer 31, the sheet resistance value of the light-shielding layer 30 can be said to be substantially the same as the sheet resistance value of the light-shielding layer 31. As described above, even if the back surface antireflection layer 33 is formed, the sheet resistance value thereof is negligibly small.
According to the study of the inventors, when the light-shielding film has high conductivity (that is, a small sheet resistance value), a discharge current flows at a burst through a part of the patterned light-shielding film (an isolated pattern or the like surrounded by a region where the transparent substrate is exposed on the outer periphery), and thus the part of the light-shielding film dissolves, and as a result, the light-shielding film pattern is considered to be damaged.
On the other hand, as proposed in the present invention, when the conductivity of the light-shielding film is low (that is, the sheet resistance value is large), even if electrostatic discharge occurs, it is difficult for a discharge current to flow through the light-shielding film pattern at once, as in the case of the light-shielding film having high conductivity, and therefore the light-shielding film pattern does not dissolve, and as a result, it is considered that the resistance to electrostatic breakdown can be improved.
By providing the light-shielding film 30 and/or the light-shielding layer 31 with a sheet resistance value in the above range, electrostatic breakdown of the large-sized and high-definition photomask 100 for manufacturing an FPD and the photomask blank 10 as a master thereof, for example, can be effectively suppressed.
The light-shielding films 30 of the photomask blanks 10 of embodiments 1 and 2 have light-shielding properties against exposure light. Specifically, the light-shielding film 30 may have an Optical Density (OD) of 2 or more. The light-shielding film 30 has an optical density of preferably 3 or more, more preferably 3.5 or more, and further preferably 4 or more. When the photomask blank 10 has another film different from the light-shielding film 30 between the light-shielding film 30 and the transparent substrate 20, the optical density of the light-shielding film 30 may be set so that the optical density of the light-shielding film 30 and the other film in a laminated state falls within the above range. The optical density can be measured using a spectrophotometer, an OD meter, or the like.
The light-shielding film 30 has a back surface reflectance of preferably 15% or less, more preferably 12% or less, and still more preferably 10% or less in a wavelength region of 365nm to 436 nm. Alternatively, the back surface reflectance of the light-shielding film 30 is preferably 15% or less, more preferably 12% or less, and still more preferably 10% or less at a typical wavelength in the wavelength region of 365nm to 436 nm. In addition, when the exposure light includes j-rays (wavelength 313 nm), the back surface reflectance of the light-shielding film 30 is preferably 15% or less, more preferably 12% or less, with respect to light in a wavelength region of 313nm to 436 nm. The back surface reflectance of the light-shielding film 30 is preferably 10% or less. Alternatively, the back surface reflectance of the light-shielding film 30 is preferably 15% or less, more preferably 12% or less, and further preferably 10% or less at a representative wavelength in the wavelength region of 313nm to 436 nm. The light-shielding film 30 has a back surface reflectance of 0.2% or more in a wavelength region of 365nm to 436nm, and preferably 0.2% or more for light in a wavelength region of 313nm to 436 nm. The surface reflectance of the light shielding film 30 is also the same.
The back surface reflectance and the surface reflectance can be measured using a spectrophotometer or the like.
The film thickness of the light-shielding film 30 is preferably 60nm or more, and more preferably 80nm or more. On the other hand, the film thickness of the light-shielding film 30 is preferably 200nm or less, more preferably 150nm or less. The thickness of the light-shielding layer 31 is preferably 50nm or more, and more preferably 60nm or more. On the other hand, the film thickness of the light-shielding layer 31 is preferably 120nm or less, and more preferably 100nm or less. The thicknesses of the front surface antireflection layer 32 and the back surface antireflection layer 33 are preferably 10nm or more. On the other hand, the film thicknesses of the front surface antireflection layer 32 and the back surface antireflection layer 33 are preferably 50nm or less.
When the light-shielding film 30 has a multilayer structure (a structure having at least one of the front anti-reflection layer 32 and the back anti-reflection layer 33), the ratio of the thickness of the light-shielding layer 31 to the thickness of the entire light-shielding film 30 is preferably 0.5 or more, more preferably greater than 0.5, and still more preferably 0.6 or more. On the other hand, the ratio of the thickness of the light-shielding layer 31 to the thickness of the entire light-shielding film 30 is preferably 0.9 or less.
The refractive index n of the light-shielding film 30 having a single-layer structure is preferably 3.0 or more at a wavelength of 405 nm. On the other hand, the refractive index n of the light-shielding film 30 having a single-layer structure is preferably 4.5 or less at a wavelength of 405 nm. The light-shielding film 30 having a single-layer structure preferably has an extinction coefficient k of 1.5 or more, more preferably 2.0 or more, under light having a wavelength of 405 nm. On the other hand, the light-shielding film 30 having a single-layer structure preferably has an extinction coefficient k of 3.5 or less, more preferably 3.0 or less, under light having a wavelength of 405 nm.
When the light-shielding film 30 has a multilayer structure (a structure having at least one of the front anti-reflection layer 32 and the back anti-reflection layer 33), the refractive index n of the light-shielding layer 31 at a wavelength of 405nm is preferably 3.0 or more. On the other hand, the refractive index n of the light-shielding layer 31 under light having a wavelength of 405nm is preferably 4.5 or less. The extinction coefficient k of the light-shielding layer 31 under light having a wavelength of 405nm is preferably 1.5 or more, and more preferably 2.0 or more. On the other hand, the extinction coefficient k of the light-shielding layer 31 under light having a wavelength of 405nm is preferably 3.5 or less, and more preferably 3.0 or less.
The refractive index n of the front anti-reflection layer 32 and the back anti-reflection layer 33 under light having a wavelength of 405nm is preferably 2.0 or more. On the other hand, the refractive index n of the front anti-reflection layer 32 and the back anti-reflection layer 33 under light having a wavelength of 405nm is preferably 2.8 or less. The extinction coefficients k of the front anti-reflection layer 32 and the back anti-reflection layer 33 under light having a wavelength of 405nm are preferably 0.2 or more. On the other hand, the extinction coefficients k of the front anti-reflection layer 32 and the back anti-reflection layer 33 under light having a wavelength of 405nm are preferably 0.8 or less.
The light shielding film 30 can be formed by a known film formation method such as a sputtering method.
< etching mask film 40>
The photomask blank 10 for manufacturing a display device according to embodiment 1 includes an etching mask film 40 having an etching selectivity different from that of the light shielding film 30 on the light shielding film 30.
The etching mask film 40 is disposed above the light-shielding film 30 (on the side opposite to the transparent substrate 20), and is made of a material having etching resistance (different from the etching selectivity of the light-shielding film 30) to an etching solution for etching the light-shielding film 30. In addition, the etching mask film 40 may have a function of blocking the exposure light from passing therethrough. Further, the etching mask film 40 may have a function of reducing the film surface reflectance so that the film surface reflectance of the light shielding film 30 with respect to light incident from the light shielding film 30 side is 15% or less in a wavelength region of 350nm to 436 nm.
The etching mask film 40 is preferably made of a chromium-based material containing chromium (Cr). The etching mask film 40 is more preferably made of a material containing chromium and substantially not containing silicon. Substantially free of silicon means that the content of silicon is less than 2 atomic% (wherein the composition gradient region of the interface of the light-shielding film 30 and the etching mask film 40 is not included). More specifically, the chromium-based material may be chromium (Cr), or a material containing chromium (Cr) and at least one of oxygen (O), nitrogen (N), and carbon (C). Further, examples of the chromium-based material include a material containing chromium (Cr), at least one of oxygen (O), nitrogen (N), and carbon (C), and further containing fluorine (F). Examples of the material constituting the etching mask film 40 include Cr, crO, crN, crF, crCO, crCN, crON, crCON, and CrCONF.
The etching mask film 40 can be formed by a known film formation method such as a sputtering method.
The etching mask film 40 may be constituted by a single film having a uniform composition depending on the function. In addition, the etching mask film 40 may be composed of a plurality of films having different compositions. In addition, the etching mask film 40 may be constituted by a single film whose composition continuously changes in the thickness direction.
Photomask blank 10 according to embodiment 1 shown in fig. 1 includes etching mask film 40 on light-shielding film 30. The photomask blank 10 according to embodiment 1 includes a photomask blank 10 having a structure in which an etching mask film 40 is provided on a light-shielding film 30 and a resist film is provided on the etching mask film 40.
< method for producing photomask blank 10 >
Next, a method for manufacturing the photomask blank 10 will be described. Photomask blank 10 according to embodiment 1 shown in fig. 1 is manufactured through a step of forming light-shielding film 30 and a step of forming etching mask film 40. Photomask blank 10 according to embodiment 2 shown in fig. 2 is manufactured through a step of forming light-shielding film 30.
The respective steps will be described in detail below.
< light-shielding film-Forming step >
First, the transparent substrate 20 is prepared. The transparent substrate 20 may be made of a material selected from the group consisting of synthetic quartz glass, aluminosilicate glass, soda-lime glass, and low thermal expansion glass (SiO) as long as it is transparent to exposure light 2 -TiO 2 Glass, etc.) and the like.
Next, the light shielding film 30 is formed on the transparent substrate 20 by a sputtering method.
The light shielding film 30 can be formed by using a predetermined sputtering target in a predetermined sputtering gas atmosphere. The predetermined sputtering target is, for example, a titanium silicide target containing titanium and silicon as main components of the material constituting the light shielding film 30, or a titanium silicide target containing titanium, silicon and nitrogen. The predetermined sputtering gas atmosphere is, for example, a sputtering gas atmosphere composed of an inert gas containing at least one selected from the group consisting of helium, neon, argon, krypton, and xenon, or a sputtering gas atmosphere composed of a mixed gas containing the above inert gas, nitrogen, and optionally a gas selected from the group consisting of oxygen, carbon dioxide, nitric oxide, and nitrogen dioxide. The light shielding film 30 can be formed in a state where the gas pressure in the film forming chamber during sputtering is 0.3Pa to 3.0Pa, preferably 0.43Pa to 2.0 Pa.
The composition and thickness of the light-shielding film 30 are adjusted so that the light-shielding film 30 attains the above optical density. The composition of the light-shielding film 30 can be controlled by the content ratio of elements constituting the sputtering target (for example, the ratio of the content of titanium to the content of silicon), the composition and flow rate of the sputtering gas, and the like. The thickness of the light shielding film 30 can be controlled by sputtering power, sputtering time, and the like. The light shielding film 30 is preferably formed by using an inline sputtering apparatus. In the case where the sputtering apparatus is an inline type sputtering apparatus, the thickness of the light shielding film 30 may be controlled by the transfer speed of the transparent substrate.
When the light shielding film 30 is formed of a single film (light shielding layer 31), the above-described film formation process is performed only once by appropriately adjusting the composition and flow rate of the sputtering gas. When the light-shielding film 30 is formed of a plurality of films having different compositions, as in the case where the light-shielding film 30 includes the light-shielding layer 31 and the front anti-reflection layer 32 and/or the back anti-reflection layer 33, the above-described film formation process is performed a plurality of times by appropriately adjusting the composition and flow rate of the sputtering gas. The light-shielding film 30 can be formed using targets having different content ratios of elements constituting the sputtering target. In the case where the film formation process is performed a plurality of times, the sputtering power applied to the sputtering target may be changed in each film formation process.
< surface treatment Process >)
The light shielding film 30 may be composed of a titanium silicide material (titanium silicide oxynitride) containing oxygen in addition to titanium, silicon, and nitrogen. Wherein the oxygen content is more than 0 atomic% and 5 atomic% or less. In the case where the light-shielding film 30 contains oxygen, a surface treatment step for adjusting the state of surface oxidation of the light-shielding film 30 may be performed on the surface of the light-shielding film 30 in order to suppress permeation of the etching solution due to the presence of titanium oxide. In the case where the light-shielding film 30 is made of a titanium silicide nitride containing titanium, silicon, and nitrogen, the content of titanium oxide is smaller than that of the titanium silicide material containing oxygen. Therefore, when the material of the light-shielding film 30 is titanium silicide nitride, the surface treatment step may be performed or not.
Examples of the surface treatment step for adjusting the surface oxidation state of the light-shielding film 30 (light-shielding layer 31 or surface anti-reflection layer 32) include a method of performing surface treatment with an acidic aqueous solution, a method of performing surface treatment with an alkaline aqueous solution, and a method of performing surface treatment with drying treatment such as ashing.
Thus, the photomask blank 10 of embodiment 2 can be obtained.
< etching mask film Forming Process >)
Photomask blank 10 of embodiment 1 further has etching mask film 40. In this case, the following etching mask film forming step is further performed. The etching mask film 40 is preferably made of a material containing chromium and substantially no silicon.
After the light-shielding film formation step, a surface treatment for adjusting the surface oxidation state of the surface of the light-shielding film 30 (the light-shielding layer 31 or the surface antireflection layer 32) is performed as necessary, and then an etching mask film 40 is formed on the light-shielding film 30 by a sputtering method. The etching mask film 40 is preferably formed using an in-line type sputtering apparatus. In the case where the sputtering apparatus is an inline type sputtering apparatus, the thickness of the etching mask film 40 may be controlled by the transport speed of the transparent substrate 20.
The etching mask film 40 can be formed using a sputtering target containing chromium or a chromium compound (chromium oxide, chromium nitride, chromium carbide, chromium oxynitride, chromium carbonitride, chromium oxycarbonitride, or the like) in a sputtering gas atmosphere composed of an inert gas or a sputtering gas atmosphere composed of a mixed gas of an inert gas and an active gas. The inactive gas may contain, for example, at least one selected from the group consisting of helium, neon, argon, krypton, and xenon. The active gas may include at least one selected from the group consisting of oxygen gas, nitrogen gas, nitric oxide gas, nitrogen dioxide gas, carbon dioxide gas, hydrocarbon-based gas, and fluorine-based gas. Examples of the hydrocarbon gas include methane gas, butane gas, propane gas, and styrene gas.
In the case where the etching mask film 40 is composed of a single film having a uniform composition, the above-described film formation process is performed only 1 time without changing the composition and flow rate of the sputtering gas. In the case where the etching mask film 40 is formed of a plurality of films having different compositions, the above-described film formation process is performed a plurality of times while changing the composition and flow rate of the sputtering gas in each film formation process. In the case where the etching mask film 40 is composed of a single film whose composition continuously changes in the thickness direction, the composition and flow rate of the sputtering gas are changed with the passage of time of the film formation process while the above-described film formation process is performed only 1 time.
In this manner, the photomask blank 10 of embodiment 1 including the etching mask film 40 can be obtained.
In addition, since photomask blank 10 according to embodiment 1 shown in fig. 1 includes etching mask film 40 on light-shielding film 30, an etching mask film forming step is performed when photomask blank 10 is manufactured. In the production of photomask blank 10 having etching mask film 40 on light-shielding film 30 and a resist film on etching mask film 40, the resist film is formed on etching mask film 40 after the etching mask film forming step. In addition, in photomask blank 10 according to embodiment 2 shown in fig. 2, when photomask blank 10 including a resist film on light-shielding film 30 is manufactured, a resist film is formed after the light-shielding film formation step.
< method for manufacturing photomask 100 >
Next, a method for manufacturing the photomask 100 will be described.
< method for manufacturing photomask 100 of embodiment 1 >
Fig. 4A to 4D are schematic views for explaining a method of manufacturing a photomask 100 using the photomask blank 10 of embodiment 1 shown in fig. 1. The method of manufacturing the photomask 100 according to embodiment 1 includes the steps of: a step of preparing a photomask blank 10; a step of forming a resist film on the etching mask film 40, and performing wet etching on the etching mask film 40 using the resist film pattern formed of the resist film as a mask to form an etching mask film pattern 40a on the light-shielding film 30; and a step of forming a transfer pattern 30a on the transparent substrate 20 by wet etching the light shielding film 30 using the etching mask film pattern 40a as a mask.
The transfer pattern in the present specification means a transfer pattern obtained by patterning at least 1 optical film formed on the transparent substrate 20. The optical film may be a light-shielding film 30, or a light-shielding film 30 and an etching mask film 40, and may further include other films (a phase shift film, a semi-transmissive film, a conductive film, and the like). That is, the transfer pattern may include a patterned light-shielding film, a patterned light-shielding film and an etching mask film, or may further include another patterned film.
Next, a method for manufacturing the photomask 100 according to embodiment 1 will be specifically described with reference to fig. 4A to 4D.
First, a resist film is formed on the etching mask film 40 of the photomask blank 10 shown in fig. 1. Next, a desired pattern is drawn and developed on the resist film, thereby forming a resist film pattern 50 (see fig. 4A, a step of forming the resist film pattern 50). Next, the etching mask film 40 is wet-etched using the resist film pattern 50 as a mask, and an etching mask film pattern 40a is formed on the light-shielding film 30 (see fig. 4B, a step of forming the etching mask film pattern 40 a). Next, the light shielding film 30 is wet-etched using the etching mask film pattern 40a as a mask, thereby forming a light shielding film pattern 30a on the transparent substrate 20 (see fig. 4C, a forming step of the light shielding film pattern 30 a). Thereafter, a process of peeling off the etching mask film pattern 40a may be further included (refer to fig. 4D).
More specifically, in the step of forming the resist pattern 50, first, a resist film is formed on the etching mask film 40 of the photomask blank 10. The resist film material used is not particularly limited. The resist film may be exposed to a laser beam having any wavelength selected from a wavelength range of 350nm to 436nm, for example. The resist film may be either a positive type or a negative type.
Then, a desired pattern is drawn on the resist film by using a laser beam having any wavelength selected from a wavelength region of 350nm to 436 nm. The pattern drawn on the resist film is a pattern formed on the light-shielding film 30. As the pattern drawn on the resist film, a line space pattern and a hole pattern can be exemplified.
Thereafter, the resist film is developed with a predetermined developing solution, and as shown in fig. 4A, a resist film pattern 50 is formed on the etching mask film 40.
< Process for Forming etching mask film Pattern 40a > >)
In the step of forming the etching mask film pattern 40a, first, the etching mask film 40 is etched using the resist film pattern 50 as a mask to form the etching mask film pattern 40a. The etching mask film 40 may be formed of a chromium-based material including chromium (Cr). The etching solution for etching the etching mask film 40 is not particularly limited as long as the etching mask film 40 can be selectively etched. Specifically, an etching solution containing cerium ammonium nitrate and perchloric acid is mentioned.
Thereafter, the resist film pattern 50 is peeled off using a resist stripping liquid or by ashing, as shown in fig. 4B. In some cases, the subsequent light shielding film pattern 30a may be formed without removing the resist film pattern 50.
< Process for Forming light-blocking film Pattern 30a > >)
In the step of forming the light shielding film pattern 30a, the light shielding film 30 is wet-etched using the etching mask film pattern 40a as a mask, thereby forming the light shielding film pattern 30a as shown in fig. 4C. As the light shielding film pattern 30a, a line space pattern and a hole pattern can be given. The etching liquid for etching the light-shielding film 30 is not particularly limited as long as the light-shielding film 30 can be selectively etched. Examples thereof include an etching solution a (an etching solution containing ammonium bifluoride and hydrogen peroxide, etc.) and an etching solution B (an etching solution containing ammonium fluoride, phosphoric acid and hydrogen peroxide, etc.).
In order to improve the sectional shape of the light shielding film pattern 30a, the wet etching is preferably performed for a time (over-etching time) longer than a time (proper amount of etching time) until the transparent substrate 20 is exposed in the light shielding film pattern 30a. In consideration of the influence on the transparent substrate 20, the overetching time is preferably a time obtained by adding 20% of the appropriate amount of etching time to the appropriate amount of etching time, and more preferably a time obtained by adding 10% of the appropriate amount of etching time.
Thereafter, the etching mask film pattern 40a is peeled off as necessary, and the photomask 100 is obtained (fig. 4D). In the case where the step of forming the light shielding film pattern 30a is performed without removing the resist pattern 50, the resist pattern 50 is removed by ashing or using a resist removing solution before the etching mask film pattern 40a is removed.
Thus, the photomask 100 can be obtained. That is, the transfer pattern of the photomask 100 according to embodiment 1 may include the light-shielding film pattern 30a, and may further include the etching mask film pattern 40a. When the etching mask film 40 is made of a chromium-based material containing chromium (Cr), the etching mask film 40 is preferably peeled from the viewpoint of improving the antistatic breakdown property.
According to the method of manufacturing photomask 100 of embodiment 1, photomask blank 10 shown in fig. 1 is used, and thus light-shielding film pattern 30a having a good edge cross-sectional shape can be formed.
In addition, the load effect in the step of forming the light shielding film pattern 30a can be reduced. Therefore, the photomask 100 capable of transferring the transfer pattern including the high-definition light shielding film pattern 30a with good accuracy can be manufactured. The photomask 100 thus manufactured can correspond to the line space pattern and/or the miniaturization of the contact hole.
As described later, the antistatic breakdown property can be improved by setting the sheet resistance value of the light shielding film pattern 30a to 40 Ω/sq or more.
< method for manufacturing photomask 100 of embodiment 2 >)
Fig. 5A to 5C are schematic views for explaining a method of manufacturing a photomask 100 using the photomask blank 10 shown in fig. 2. The method for manufacturing the photomask 100 according to embodiment 2 includes the steps of: a step of preparing a photomask blank 10; and a step of forming a resist film on the light-shielding film 30, and wet-etching the light-shielding film 30 using a resist pattern formed of the resist film as a mask to form a transfer pattern on the transparent substrate 20.
Next, a method for manufacturing the photomask 100 according to embodiment 2 will be specifically described with reference to fig. 5A to 5C.
First, a resist film is formed on photomask blank 10 shown in fig. 2. Next, a desired pattern is drawn and developed on the resist film, thereby forming a resist film pattern 50 (fig. 5A, a resist film pattern 50 forming step). Next, the light-shielding film 30 is wet-etched using the resist film pattern 50 as a mask, thereby forming a light-shielding film pattern 30a on the transparent substrate 20 (fig. 5B and 5C, a forming step of the light-shielding film pattern 30 a).
More specifically, in the step of forming a resist pattern, first, a resist film is formed on the light-shielding film 30 of the photomask blank 10 according to embodiment 2 shown in fig. 2. The resist film material used is the same as that described above. Before the resist film is formed, the light-shielding film 30 (light-shielding layer 31 or surface antireflection layer 32) may be subjected to surface modification treatment as necessary to improve adhesion between the light-shielding film 30 and the resist film. After the resist film is formed in the same manner as described above, a desired pattern is drawn on the resist film using, for example, a laser beam having any wavelength selected from a wavelength region of 350nm to 436 nm. Thereafter, the resist film is developed with a predetermined developer, and as shown in fig. 5A, a resist film pattern 50 is formed on the light-shielding film 30.
< Process for Forming light-blocking film Pattern 30a > >)
In the light-shielding film pattern 30a forming step, the light-shielding film 30 is etched using the resist film pattern 50 as a mask, and as shown in fig. 5B, a light-shielding film pattern 30a is formed. The etching solution and the overetching time for etching the light-shielding film 30 are the same as those described in the embodiment shown in fig. 4C.
After that, the resist film pattern 50 is peeled off using a resist stripper or by ashing (fig. 5C).
Thus, the photomask 100 can be obtained. The transfer pattern of the photomask 100 according to embodiment 2 is composed of only the light-shielding film pattern 30a, but may further include another film pattern. Examples of the other film include a phase shift film, a semi-transparent film, and a conductive film.
According to the method of manufacturing photomask 100 of embodiment 2, photomask blank 10 shown in fig. 2 is used, and thus light-shielding film pattern 30a having a good edge cross-sectional shape can be formed.
In addition, the load effect in the step of forming the light shielding film pattern 30a can be reduced. Therefore, the photomask 100 capable of transferring the transfer pattern including the high-definition light shielding film pattern 30a with good accuracy can be manufactured. The photomask 100 thus manufactured can correspond to the line space pattern and/or the miniaturization of the contact hole.
As described later, the antistatic breakdown property can be improved by setting the sheet resistance value of the light shielding film pattern 30a to 40 Ω/sq or more.
< method for producing display device >
A method for manufacturing a display device according to embodiment 1 and embodiment 2 will be described. The method for manufacturing the display device according to embodiments 1 and 2 includes the following exposure steps: the photomask 100 of the above-described embodiment is placed on a mask stage of an exposure apparatus, and a transfer pattern formed on the photomask 100 is exposed and transferred to a resist film formed on a substrate for a display device.
Specifically, the method for manufacturing the display device according to embodiment 1 or 2 includes the steps of: a step of placing the photomask 100 manufactured using the photomask blank 10 on a mask stage of an exposure apparatus (mask placing step); and a step (exposure step) of exposing and transferring the transfer pattern to a resist film on a substrate for a display device. The respective steps will be described in detail below.
< mask mounting step >)
In the mask placing step, the photomask 100 according to embodiments 1 and 2 is placed on the mask stage of the exposure apparatus. Here, the photomask 100 is disposed so as to face a resist film formed on a substrate for a display device by a projection optical system of an exposure apparatus.
< Pattern transfer Process >)
In the pattern transfer step, the photomask 100 is irradiated with exposure light, and a transfer pattern including the light-shielding film pattern 30a is transferred to a resist film formed on a substrate for a display device. The exposure light is a composite light including light having a plurality of wavelengths selected from a wavelength region of 313nm to 436nm, a monochromatic light selected by cutting a certain wavelength region from the wavelength region of 313nm to 436nm by a filter or the like, or a monochromatic light emitted from a light source having a wavelength region of 313nm to 436 nm. For example, the exposure light is a composite light including at least one of an i-ray, an h-ray, and a g-ray, or a monochromatic light of an i-ray. By using the composite light as the exposure light, the exposure light intensity can be increased, and the productivity can be improved. Therefore, the manufacturing cost of the display device can be reduced.
According to the methods of manufacturing the display devices of embodiments 1 and 2, a high-definition display device having a high-resolution, fine line space pattern and/or contact holes can be manufactured.
Examples
The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.
Example 1.
A. Photomask blank and method for manufacturing same
To manufacture the photomask blank of example 1, first, a synthetic quartz glass substrate of 1214 size (1220 mm × 1400 mm) was prepared as the transparent substrate 20.
Thereafter, the synthetic quartz glass substrate was mounted on a tray (not shown) with its main surface facing downward, and was carried into a chamber of a line-type sputtering apparatus.
To form the light-shielding layer 31 as the light-shielding film 30 on the main surface of the transparent substrate 20, first, argon (Ar) gas is introduced into the 1 st chamber. Then, a predetermined sputtering power is applied to the 1 st sputtering target (titanium: silicon = 1) containing titanium and silicon, and sputtering is performed, thereby forming the light-shielding film 30 (light-shielding layer 31) of titanium silicide composed of titanium and silicon on the main surface of the transparent substrate 20.
Subsequently, the transparent substrate 20 with the light-shielding layer 31 formed thereon is carried into the 2 nd chamber, and argon (Ar) gas and nitrogen (N) gas are introduced into the 2 nd chamber 2 ) Gas is a mixed gas. Then, a predetermined sputtering power is applied to the 2 nd sputtering target made of chromium, and reactive sputtering is performed, thereby forming the etching mask film 40 containing chromium nitride of chromium and nitrogen on the light shielding layer 31.
Thus, photomask blank 10 in which light-shielding film 30 made of only light-shielding layer 31 and etching mask film 40 were formed on transparent substrate 20 was obtained.
Various characteristics of the light-shielding film 30 in the obtained photomask blank 10 were measured as follows.
[ Optical Density (OD) ]
The light density (OD) of the light-shielding film 30 composed only of the light-shielding layer 31 was measured by a spectrophotometer, and found to be 3.6 (wavelength 405 nm). In order to measure the optical density of the light-shielding film 30, a substrate with a light-shielding film (dummy substrate) was used, which was manufactured on the same tray, and the light-shielding film 30 composed only of the light-shielding layer 31 was formed on the main surface of the synthetic quartz glass substrate. The optical density of the light-shielding film 30 is measured by taking out the substrate with the light-shielding film (dummy substrate) from the chamber before the etching mask film 40 is formed.
[ sheet resistance ]
The sheet resistance of the light-shielding film 30 of example 1 was measured by a four-terminal method using the dummy substrate, and was 62.9 Ω/sq.
Further, the light-shielding film 30 was subjected to composition analysis in the depth direction by X-ray photoelectron spectroscopy (XPS). The dummy substrate was used for the actual measurement. As a result, the light-shielding film 30 has substantially constant contents of the respective constituent elements in the depth direction except for a composition gradient region at the interface between the transparent substrate 20 and the light-shielding film 30. The specific film composition (atomic%) was 38% titanium, 55% silicon, 5% nitrogen and 2% oxygen.
B. Photomask and method for manufacturing the same
To manufacture the photomask 100 using the photomask blank 10 manufactured as above, first, a photoresist is applied onto the etching mask film 40 of the photomask blank 10 using a resist coating apparatus.
Then, a photoresist film is formed through heating and cooling steps.
After that, a photoresist film is drawn by a laser drawing device, and a resist film pattern 50 including a line space pattern is formed on the etching mask film 40 through a developing and rinsing process.
Thereafter, the etching mask film 40 is wet-etched using a Cr etching solution containing cerium ammonium nitrate and perchloric acid with the resist film pattern 50 as a mask, thereby forming an etching mask film pattern 40a. Then, the resist film pattern 50 is peeled off. Next, the light-shielding film 30 is wet-etched with a titanium silicide etchant obtained by diluting a mixed solution of ammonium bifluoride and hydrogen peroxide with pure water, using the etching mask film pattern 40a as a mask, to form a light-shielding film pattern 30a. Further, the etching mask film 40 is peeled off by the Cr etching liquid.
The obtained photomask 100 was tested for its load effect during manufacture. First, by the above method, a photomask 100 including a plurality of line space (L & S) patterns having a pattern pitch of 4 μm, a light-transmitting region (region where the transparent substrate is exposed) surrounding the outer periphery of the plurality of line space patterns, and a light-shielding region surrounding the outer periphery of the light-transmitting region was prepared (see fig. 6). In fig. 6, a white area indicates a light shielding film pattern (line pattern and light shielding area), and a gray area indicates a space pattern and a light transmitting area. In the test on the load effect, the etching mask film was in a state of being present on the light shielding film pattern 30a (line pattern and light shielding region). Other examples and comparative examples are also the same. In the etching of the light-shielding film 30, in order to clarify the presence or absence of the load effect and the difference in the degree, the overetching time was 200% with respect to the proper amount of etching time.
In example 1, as shown in fig. 6, the ratio P1/P3 of the side etching amount P1 of the light-shielding film 30 at the dense pattern point 1 (the amount of retreat of the edge of the line pattern formed by the light-shielding film 30) to the side etching amount P3 of the light-shielding film 30 at the sparse pattern point 3 (the amount of retreat of the edge on the outer frame side of the light-shielding tape formed by the light-shielding film 30) was calculated, and the degree of the load effect was confirmed. The side-etching amount (the amount of receding of the edge) refers to how much the light-shielding film 30 is side-etched from the edge position of the etching mask film pattern 40a. Specifically, in the cross-sectional view of the photomask 100, the side etching amount is determined by calculating the distance (dimension) from the edge of the etching mask film pattern 40a to the edge of the light shielding film 30.
P1/P3 refers to the ratio of the etch rate at point 1 relative to the etch rate at point 3. The closer P1/P3 is to 1, the smaller the difference in etching rate between the point 1 and the point 3, and it can be said that the load effect can be reduced. The amount of side etching at point 1 is preferably within ± 20% of the amount of side etching at point 3. Thus, it can be determined that: if the ratio P1/P3 of the etching rates is in the range of 0.8 to 1.2, the load effect can be reduced favorably, and if P1/P3 is less than 0.8 or more than 1.2, the load effect cannot be reduced favorably.
In photomask 100 using photomask blank 10 of example 1, P1/P3 was 0.93. That is, it is found that the photomask blank 10 of example 1 can reduce the load effect well. In addition, the obtained photomask was subjected to an electrostatic breakdown test, and favorable results were obtained.
Example 2.
A. Photomask blank and method for manufacturing same
In order to manufacture the photomask blank of example 2, a synthetic quartz glass substrate having a size of 1214 (1220 mm × 1400 mm) was prepared as a transparent substrate in the same manner as in example 1.
In the same manner as in example 1, the synthetic quartz glass substrate was carried into the chamber of the inline sputtering apparatus. Then, argon (Ar) gas and nitrogen (N) are introduced into the 1 st chamber 2 ) Gas is a mixed gas. Then, a 1 st sputtering target (titanium: silicon =1 3) containing titanium and silicon was applied with a predetermined sputtering power and subjected to reactive sputtering, thereby forming a back surface antireflection layer 33 of a nitride of titanium silicide containing titanium, silicon, and nitrogen on the main surface of the transparent substrate 20 (fig. 3).
Next, the transparent substrate 20 on which the back surface antireflection layer 33 is formed is carried into the 2 nd chamber. Argon (Ar) gas is introduced into the 2 nd chamber. Then, a predetermined sputtering power is applied to a 2 nd sputtering target (titanium: silicon =1 3) containing titanium and silicon, and sputtering is performed, thereby forming a light-shielding layer 31 of titanium silicide made of titanium and silicon on the back surface antireflection film 33.
Then, the transparent substrate 20 on which the back surface antireflection layer 33 and the light shielding layer 31 are formed is carried into the 3 rd chamber. Introducing argon (Ar) gas and nitrogen (N) into the 3 rd chamber 2 ) Gas is a mixed gas. Then, a predetermined sputtering power is applied to a 3 rd sputtering target (titanium: silicon =1 3) containing titanium and silicon, and a surface antireflection layer 32 of a nitride of titanium silicide containing molybdenum, silicon, and nitrogen is formed on the light shielding layer 31 by reactive sputtering.
Then, the transparent substrate 20 having the antireflection layer 32 formed thereon is carried into the 4 th chamber, and argon (Ar) gas and nitrogen (N) gas are introduced into the 4 th chamber 2 ) Gas is a mixed gas. Then, a predetermined sputtering power is applied to the 4 th sputtering target made of chromium, and reactive sputtering is performed, thereby forming an etching mask film 40 of chromium nitride containing chromium and nitrogen on the surface antireflection layer 32.
Thus, photomask blank 10 was obtained in which light-shielding film 30 and etching mask film 40 having a laminated structure of back surface anti-reflection layer 33, light-shielding layer 31 and front surface anti-reflection layer 32 were formed on transparent substrate 20.
The optical density of the light-shielding film 30 having a laminated structure of the back surface anti-reflection layer 33, the light-shielding layer 31, and the surface anti-reflection layer 32 in the obtained photomask blank 10 was measured with a spectrophotometer, and found to be 4.9 (wavelength 405 nm). The sheet resistance of the light-shielding film 30 of example 2 was measured in the same manner as in example 1, and found to be 42.8 Ω/sq. In the same manner as in example 1, a substrate with a light-shielding film (dummy substrate) prepared by being set on the same tray and having the light-shielding film 30 formed on the main surface of the synthetic quartz glass substrate was used for measuring the optical density and the sheet resistance of the light-shielding film 30.
Further, the light-shielding film 30 was subjected to composition analysis in the depth direction by X-ray photoelectron spectroscopy (XPS). The dummy substrate was used for the actual measurement. As a result, in the light-shielding film 30, the content of each constituent element in each layer is substantially constant in the depth direction except for the composition gradient region of the interface between the transparent substrate 20 and the back surface anti-reflection layer 33, the composition gradient region of the interface between the back surface anti-reflection layer 33 and the light-shielding layer 31, and the composition gradient region of the interface between the light-shielding layer 31 and the front surface anti-reflection layer 32. In a specific film composition, the light-shielding layer 31 contains 37 atomic% of titanium, 60 atomic% of silicon, and 3 atomic% of nitrogen. In the surface antireflection layer 32, titanium was 10 atomic%, silicon was 37 atomic%, and nitrogen was 53 atomic%. In the back surface antireflection layer 33, titanium was 10 atomic%, silicon was 37 atomic%, and nitrogen was 53 atomic%.
The light-shielding film 30 has a surface reflectance of 3.3% (wavelength 405 nm) and a back surface reflectance of 4% (wavelength 405 nm). That is, the photomask blank 10 of example 2 can improve the accuracy at the time of pattern writing or pattern transfer.
B. Photomask and method for manufacturing the same
To manufacture photomask 100 using photomask blank 10 manufactured as described above, first, a photoresist is applied to etching mask film 40 of photomask blank 10 using a resist application apparatus.
Then, a photoresist film is formed through heating and cooling steps.
After that, a photoresist film is drawn by a laser drawing device, and a resist film pattern 50 including a line space pattern is formed on the etching mask film through a developing and rinsing process.
Thereafter, the etching mask film 40 is wet-etched using a Cr etching solution containing cerium ammonium nitrate and perchloric acid with the resist film pattern 50 as a mask, thereby forming an etching mask film pattern 40a. Then, the resist film pattern 50 is peeled off. Next, the light-shielding film 30 is wet-etched with a titanium silicide etchant obtained by diluting a mixed solution of ammonium bifluoride and hydrogen peroxide with pure water, using the etching mask film pattern 40a as a mask, to form a light-shielding film pattern 30a. Further, the etching mask film pattern 40a is peeled off by the Cr etching liquid.
The same test as in example 1 was performed for the load effect in the production of the obtained photomask 100, and as a result, the same result as that of the photomask blank 10 of example 1 was obtained also in the photomask 100 using the photomask blank 10 of example 2. The photomask obtained also had good resistance to electrostatic breakdown as compared with example 1. Therefore, the photomask 100 of example 2 can be said to have high resistance to electrostatic breakdown while reducing the loading effect well.
Comparative example 1.
A. Photomask blank and method for manufacturing same
In order to manufacture the photomask blank of comparative example 1, a synthetic quartz glass substrate having a size of 1214 (1220 mm × 1400 mm) was prepared as a transparent substrate in the same manner as in example 1, and the synthetic quartz glass substrate was carried into a chamber of an inline sputtering apparatus.
As the sputtering target, a Cr (chromium) target material was used. Then, as a sputtering gas, ar gas and N were mixed 2 Introducing a gas mixture into the chamber to form a CrN (chromium nitride) layer, and then introducing Ar gas and CH 4 A CrC layer was formed using a gas as a sputtering gas, and then a CrON layer was continuously formed to a thickness of 25nm using Ar gas and NO gas as sputtering gases. Such asThus, photomask blank 10 having light-shielding film 30 formed on transparent substrate 20 was obtained.
The optical density of the light-shielding film 30 in the obtained photomask blank 10 was measured by a spectrophotometer, and it was 3.0 (wavelength 405 nm). The sheet resistance of the light-shielding film 30 of example 2 was measured in the same manner as in example 1, and found to be 23 Ω/sq. In the same manner as in example 1, a substrate with a light-shielding film (dummy substrate) prepared by placing on the same tray and having the light-shielding film 30 formed on the main surface of the synthetic quartz glass substrate was used for the measurement of the optical density and the sheet resistance of the light-shielding film 30.
B. Photomask and method for manufacturing the same
To manufacture photomask 100 using photomask blank 10 manufactured as described above, first, a photoresist is applied onto light-shielding film 30 of photomask blank 10 using a resist coating apparatus.
Then, a photoresist film is formed through heating and cooling steps.
Then, a photoresist film is drawn by a laser drawing device, and a resist film pattern 50 including a line space pattern is formed on the light-shielding film through a developing and rinsing step.
Thereafter, the light-shielding film 30 is wet-etched using a Cr etching solution containing cerium ammonium nitrate and perchloric acid, with the resist film pattern 50 as a mask, to form a light-shielding film pattern 30a. Further, the resist film pattern 50 is peeled off.
The same test as in example 1 was performed with respect to the load effect at the time of manufacturing the obtained photomask 100. As a result, the ratio P1/P3 was 1.3. That is, in the photomask 100 using the photomask blank 10 of comparative example 1, the load effect cannot be reduced. Therefore, it can be said that the photomask blank 10 of comparative example 1 is insufficient to form a fine pattern with good accuracy.
Further, the resistance of the obtained photomask to electrostatic breakdown was also examined, and as a result, breakdown of the light-shielding film pattern was found. That is, it cannot be said that the photomask blank 10 and the photomask 100 of comparative example 1 have sufficient resistance to electrostatic breakdown.
Comparative example 2.
A. Photomask blank and method for manufacturing same
In order to manufacture the photomask blank of comparative example 2, a synthetic quartz glass substrate having a size of 1214 (1220 mm × 1400 mm) was prepared as a transparent substrate in the same manner as in example 1. Then, the synthetic quartz glass substrate (transparent substrate 20) was carried into a chamber of an inline sputtering apparatus. In order to form the light-shielding film 30 on the main surface of the synthetic quartz glass substrate, first, a mixed gas of argon (Ar) gas and helium (He) gas is introduced into the 1 st chamber. Then, a 1 st sputtering target (molybdenum: silicon =1 = 4) containing molybdenum and silicon was subjected to sputtering with a predetermined sputtering power, thereby forming a molybdenum silicide light-shielding layer 31 made of molybdenum and silicon on the main surface of the transparent substrate 20.
Next, the transparent substrate 20 on which the light-shielding layer 31 is formed is carried into the 2 nd chamber, and a mixed gas of argon (Ar) gas, nitric Oxide (NO) gas, and helium (He) gas is introduced into the 2 nd chamber. Then, a 2 nd sputtering target (molybdenum: silicon =1 = 4) containing molybdenum and silicon is applied with a predetermined sputtering power and reactive sputtering is performed, thereby forming a surface antireflection layer 32 of an oxynitride of molybdenum silicide containing molybdenum, silicon, oxygen, and nitrogen on the light shielding layer 31.
Then, the transparent substrate 20 having the light-shielding layer 31 and the surface antireflection layer 32 formed thereon is carried into the 3 rd chamber, and argon (Ar) gas and nitrogen (N) gas are introduced into the 3 rd chamber 2 ) Gas is a mixed gas. Then, a predetermined sputtering power is applied to the 3 rd sputtering target made of chromium, and reactive sputtering is performed, thereby forming the etching mask film 40 of chromium nitride containing chromium and nitrogen on the surface antireflection layer 32.
Thus, a photomask blank in which the light-shielding film 30 and the etching mask film 40 are formed on the transparent substrate 20 is obtained.
The optical density of the light-shielding film in the obtained photomask blank was measured using the dummy substrate in the same manner as in example 1 with a spectrophotometer and found to be 4.0 (wavelength 405 nm). The sheet resistance of the light-shielding film 30 of comparative example 2 was measured using the dummy substrate, and found to be 80 Ω/sq.
B. Photomask and method for manufacturing the same
In order to manufacture a photomask using the photomask blank manufactured as described above, first, a photoresist is applied to the surface of the light-shielding film (the surface of the surface antireflection layer) using a resist coating apparatus. Then, a photoresist film is formed through a heating and cooling process. After that, a photoresist film is drawn by a laser drawing device, and a resist film pattern 50 including a line space pattern is formed on the etching mask 40 film through a developing and rinsing process.
Thereafter, the etching mask film 40 is wet-etched using a Cr etching solution containing cerium ammonium nitrate and perchloric acid with the resist film pattern 50 as a mask, thereby forming an etching mask film pattern 40a. Then, the resist film pattern 50 is peeled off. Next, the light shielding film 30 is wet-etched with a molybdenum silicide etching solution obtained by diluting a mixed solution of ammonium bifluoride and hydrogen peroxide with pure water using the etching mask film pattern 40a as a mask, thereby forming a light shielding film pattern 30a. Further, the etching mask film pattern 40a is peeled off by the Cr etching liquid.
The same test as in example 1 was performed with respect to the load effect at the time of manufacturing the obtained photomask 100. As a result, in the photomask 100 using the photomask blank 10 of comparative example 2, the ratio P1/P3 was a value 0.25 largely different from 1.0, and the load effect could not be reduced.
Further, the resistance of the obtained photomask to electrostatic breakdown was also examined, and as a result, the sheet resistance of comparative example 2 was 40 Ω/sq or more, and thus the photomask had sufficient resistance to electrostatic breakdown as in example 1. However, as described above, in comparative example 2, the ratio P1/P3 is a value much smaller than 1.0, and the load effect cannot be reduced. That is, it can be said that the photomask blank 10 of comparative example 2 is insufficient to form a fine pattern with good accuracy.
Description of the symbols
10. Photomask blank
20. Transparent substrate
30. Shading film (film for pattern formation)
30a light shielding film pattern
31. Light shielding layer
32. Surface anti-reflection layer
33. Back side anti-reflection layer
40. Etching mask film
50. Resist film pattern
100. Photomask and method of manufacturing the same

Claims (25)

1. A photomask blank comprising a transparent substrate and a light-shielding film provided on the transparent substrate,
the light shielding film contains titanium (Ti) and silicon (Si),
the light-shielding film has a sheet resistance value of 40 Ω/sq or more.
2. The photomask blank according to claim 1, wherein the light-shielding film has a sheet resistance value of 90 Ω/sq or less.
3. The photomask blank of claim 1, wherein the light-shielding film comprises a light-shielding layer composed of a titanium silicide-based material containing titanium (Ti) and silicon (Si),
the light-shielding layer has a sheet resistance value of 40 Ω/sq or more.
4. The photomask blank of claim 3, wherein the light-shielding layer has a sheet resistance value of 90 Ω/sq or less.
5. The photomask blank according to claim 1, wherein the light-shielding film comprises a light-shielding layer composed of a titanium silicide-based material containing titanium (Ti) and silicon (Si),
the light-shielding layer further contains nitrogen (N) or oxygen (O).
6. The photomask blank of claim 1, wherein the light-shielding film comprises a light-shielding layer composed of a titanium silicide-based material containing titanium (Ti) and silicon (Si),
a surface anti-reflection layer is provided on the light-shielding layer.
7. The photomask blank of claim 6, wherein the surface anti-reflection layer is composed of a titanium silicide-based material containing titanium (Ti) and silicon (Si), and contains nitrogen (N) or oxygen (O).
8. The photomask blank according to any one of claims 1 to 7, wherein the light-shielding film comprises a light-shielding layer composed of a titanium silicide-based material containing titanium (Ti) and silicon (Si),
a back surface antireflection layer is provided between the transparent substrate and the light shielding layer.
9. The photomask blank of claim 8, wherein the back anti-reflection layer is composed of a titanium silicide-based material containing titanium (Ti) and silicon (Si), and contains nitrogen (N) or oxygen (O).
10. The photomask blank of claim 1, wherein the light-shielding film has thereon an etching mask film having an etching selectivity different from that of the light-shielding film.
11. The photomask blank of claim 10, wherein the etch mask film comprises chromium (Cr).
12. The photomask blank of claim 11, wherein the etch mask film further comprises nitrogen (N) or oxygen (O).
13. A photomask having a transparent substrate and a light-shielding film provided on the transparent substrate and having a transfer pattern, characterized in that,
the light shielding film contains titanium (Ti) and silicon (Si),
the light-shielding film has a sheet resistance value of 40 Ω/sq or more.
14. The photomask according to claim 13, wherein the light-shielding film has a sheet resistance value of 90 Ω/sq or less.
15. The photomask of claim 13, wherein the light-shielding film comprises a light-shielding layer composed of a titanium silicide-based material containing titanium (Ti) and silicon (Si),
the light-shielding layer has a sheet resistance value of 40 Ω/sq or more.
16. The photomask of claim 15, wherein the light-shielding layer has a sheet resistance value of 90 Ω/sq or less.
17. The photomask of claim 13, wherein the light-shielding film comprises a light-shielding layer composed of a titanium silicide-based material containing titanium (Ti) and silicon (Si),
the light-shielding layer further contains nitrogen (N) or oxygen (O).
18. The photomask of claim 13, wherein the light-shielding film comprises a light-shielding layer composed of a titanium silicide-based material containing titanium (Ti) and silicon (Si),
a surface anti-reflection layer is provided on the light-shielding layer.
19. The photomask of claim 18, wherein the surface anti-reflection layer is formed of a titanium silicide-based material containing titanium (Ti) and silicon (Si), and contains nitrogen (N) or oxygen (O).
20. The photomask of any one of claims 13 to 19, wherein the light-shielding film comprises a light-shielding layer composed of a titanium silicide-based material containing titanium (Ti) and silicon (Si),
a back surface antireflection layer is provided between the transparent substrate and the light shielding layer.
21. The photomask of claim 20, wherein the back anti-reflection layer is formed of a titanium silicide-based material containing titanium (Ti) and silicon (Si), and contains nitrogen (N) or oxygen (O).
22. A method for manufacturing a photomask, comprising the steps of:
preparing a photomask blank according to any one of claims 1 to 9; and
and a step of forming a transfer pattern on the transparent substrate by wet etching the light-shielding film using a resist film pattern provided on the light-shielding film as a mask.
23. A method for manufacturing a photomask, comprising the steps of:
preparing a photomask blank according to any one of claims 10 to 12;
a step of performing wet etching on the etching mask film using a resist film pattern provided on the etching mask film as a mask to form an etching mask film pattern on the light-shielding film; and
and a step of forming a transfer pattern on the transparent substrate by wet etching the light-shielding film using the etching mask film pattern as a mask.
24. A method for manufacturing a display device, comprising the following exposure steps: the photomask obtained by the method for manufacturing a photomask according to claim 22 or 23 is placed on a mask stage of an exposure apparatus, and the transfer pattern formed on the photomask is exposed and transferred to a resist formed on a substrate for a display device.
25. A method for manufacturing a display device, comprising the following exposure steps: the photomask according to claim 13 is placed on a mask stage of an exposure apparatus, and the transfer pattern formed on the photomask is exposed and transferred to a resist formed on a substrate for a display device.
CN202211150078.2A 2021-09-30 2022-09-21 Photomask blank, photomask, method for manufacturing photomask, and method for manufacturing display device Pending CN115903365A (en)

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JP2022131956A JP2023051759A (en) 2021-09-30 2022-08-22 Photomask blank, photomask, manufacturing method of photomask, and manufacturing method of display device

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