WO2019177116A1 - Photomasque de grande taille - Google Patents

Photomasque de grande taille Download PDF

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Publication number
WO2019177116A1
WO2019177116A1 PCT/JP2019/010647 JP2019010647W WO2019177116A1 WO 2019177116 A1 WO2019177116 A1 WO 2019177116A1 JP 2019010647 W JP2019010647 W JP 2019010647W WO 2019177116 A1 WO2019177116 A1 WO 2019177116A1
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WO
WIPO (PCT)
Prior art keywords
light
film
pattern
low
shielding
Prior art date
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PCT/JP2019/010647
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English (en)
Japanese (ja)
Inventor
冬木 今野
建也 三好
Original Assignee
大日本印刷株式会社
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 大日本印刷株式会社 filed Critical 大日本印刷株式会社
Priority to KR1020247010297A priority Critical patent/KR20240046289A/ko
Priority to CN201980032507.6A priority patent/CN112119352A/zh
Priority to JP2020506656A priority patent/JP7420065B2/ja
Priority to KR1020207029308A priority patent/KR102653366B1/ko
Publication of WO2019177116A1 publication Critical patent/WO2019177116A1/fr
Priority to JP2023182390A priority patent/JP2024001250A/ja

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
    • G03F1/38—Masks having auxiliary features, e.g. special coatings or marks for alignment or testing; Preparation thereof
    • G03F1/46—Antireflective coatings
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
    • G03F1/54—Absorbers, e.g. of opaque materials
    • G03F1/58—Absorbers, e.g. of opaque materials having two or more different absorber layers, e.g. stacked multilayer absorbers

Definitions

  • the present disclosure relates to a large-sized photomask used for manufacturing a display device functional element used in a display device.
  • a photolithography method using a photomask has been suitably used as a fine processing method at the time of manufacturing a functional element for a display device.
  • a photomask a photomask having a light-shielding pattern provided on the surface of a light-transmitting substrate and including a light-transmitting region and a light-shielding region is generally used.
  • Patent Document 1 describes a configuration of a photomask in which an antireflection film is provided on the surface side of a light shielding pattern.
  • FIG. 11 is a graph comparing the fluctuation of the transfer line width shift with respect to the exposure amount between an existing low-sensitivity resist and a high-sensitivity resist used in recent years. As shown in FIG. 11, the high-sensitivity resist has a smaller exposure amount necessary for curing than the low-sensitivity resist, and the transfer line width shift varies greatly at a stage where the exposure amount is small.
  • the exposure light including g-line, h-line, or i-line lacks the energy of exposure light applied to the resist layer. It is required to use exposure light including light of a plurality of wavelengths such as rays, h-rays, and i-rays, and in particular, it is required to use exposure light including j-rays having high energy among these lights. It has been. On the other hand, when these exposure lights are used, since the change of the resist layer during exposure increases, the influence of the above-described weak stray light on the resist layer is further increased.
  • the present disclosure has been made in view of the above-described problems, and has as its main purpose to provide a large-sized photomask that can suppress unevenness and dimensional variation in a pattern transferred to a transfer target. To do.
  • the present disclosure provides a large-sized photomask that includes a light-transmitting substrate and a light-shielding pattern provided on a surface of the light-transmitting substrate.
  • the film, the light-shielding film, and the second low-reflection film have a laminated structure in which the light-transmitting substrate side is laminated in this order, and the surface of the light-shielding pattern on the light-transmitting substrate side is 313 nm to 436 nm.
  • a large-sized photomask having a reflectance of 8% or less with respect to light in the wavelength region is provided.
  • the surface of the light shielding pattern opposite to the light transmitting substrate preferably has a reflectance of 10% or less with respect to light in the wavelength region of 313 nm to 436 nm.
  • the light-shielding film contains chromium
  • the first low-reflection film and the second low-reflection film contain chromium oxide.
  • the light shielding pattern preferably has an optical density (OD) of 4.5 or more for light in the wavelength region of 313 nm to 436 nm.
  • the inclination angle of the side surface of the light-shielding film with respect to the light-transmitting substrate is preferably 80 degrees or more and 90 degrees or less. It is because the influence of the reflected light of the exposure light irradiated on the side surface of the light shielding film can be suppressed.
  • the side surface of the first low-reflection film or the side surface of the second low-reflection film protrudes in a direction parallel to the surface of the light-transmitting substrate with respect to the side surface of the light-shielding film. Is preferred.
  • both the side surface of the first low-reflection film and the side surface of the second low-reflection film protrude in a direction parallel to the surface of the light-transmitting substrate with respect to the side surface of the light-shielding film. It is preferable that the side surface of the 1 low reflective film protrudes in a direction parallel to the surface of the translucent substrate from the side surface of the second low reflective film.
  • At least a side surface of the first low-reflection film protrudes in a direction parallel to the surface of the light-transmitting substrate with respect to a side surface of the light-shielding film, and further, the light-transmitting property on the side surface of the first low-reflection film
  • the angle with respect to the surface of the conductive substrate is preferably 56 ° or less. This is because the foreign matter can be easily removed by cleaning, and the amount of foreign matter present can be reduced.
  • the side surface of the light-shielding film is concave.
  • segmentation exposure it is preferable to have the division pattern used for division
  • FIG. 1 It is a schematic sectional drawing which shows an example of the large sized photomask of this indication. It is a schematic sectional drawing which shows the process of transferring a pattern to the resist layer which a to-be-transferred body has by exposure using the large sized photomask shown by FIG. It is the enlarged view which showed the area
  • FIG. 10 is a schematic process cross-sectional view showing a part of the manufacturing process of the pattern transfer body shown in FIG. 9. It is the graph which compared the fluctuation
  • the large-sized photomask of the present disclosure is a large-sized photomask including a light-transmitting substrate and a light-shielding pattern provided on the surface of the light-transmitting substrate.
  • the light-shielding pattern includes a first low-reflection film, a light-shielding property,
  • the film and the second low reflection film have a laminated structure in which the light transmissive substrate side is laminated in this order, and the surface of the light shielding pattern on the light transmissive substrate side has a wavelength region of 313 nm to 436 nm.
  • the reflectance with respect to light is 8% or less.
  • FIG. 1 is a schematic cross-sectional view illustrating an example of a large photomask according to the present disclosure.
  • FIG. 2 is a schematic cross-sectional view showing a process of transferring a pattern to a resist layer of a transfer target by exposure using the large photomask shown in FIG.
  • the large photomask 100 includes a translucent substrate 110 and a light shielding pattern 120 provided on the surface 110 a of the translucent substrate 110.
  • the light shielding pattern 120 has a laminated structure in which a first low reflective film 122, a light shielding film 124, and a second low reflective film 126 are laminated in this order from the light transmitting substrate 110 side.
  • the reflectance of the surface 120a of the light shielding pattern 120 on the light transmitting substrate 110 side is 8% or less for any light in the wavelength region of 313 nm to 436 nm.
  • a resist layer 220 is formed on the substrate 210 by exposure using a large photomask 100 to emit exposure light including light in any of the above wavelength regions from a light source (UV lamp).
  • the exposure light includes the surface 120a of the light shielding pattern 120 on the light transmitting substrate 110 side, the surface 300a of the exposure shielding plate 300, and the light transmitting substrate 110.
  • the exposure shielding plate 300 originally blocks the exposure light irradiation.
  • the intensity of the stray light La applied to the resist layer 220 can be reduced, for example, to less than 0.3% of the exposure illuminance. Thereby, it is possible to suppress the occurrence of unevenness and variation in dimensions in the pattern transferred to the resist layer 220 in the shielding region.
  • the exposure light is reflected due to reflection of the surface of the light shielding pattern on the light transmitting substrate side.
  • the intensity of stray light it is possible to suppress the occurrence of unevenness and dimensional variations in the pattern transferred to the transfer target.
  • g-line wavelength 436 nm
  • h-line wavelength 405 nm
  • i-line wavelength 365 nm
  • j-line wavelength 313 nm
  • the change in the resist layer during exposure by exposure light including light of a plurality of wavelengths is larger than that of exposure light of a single wavelength, and in particular, the change in resist layer during exposure by exposure light including j-rays is large. Become. For this reason, when exposure light containing light of a plurality of wavelengths, particularly exposure light containing j-rays, is used, the influence of weak stray light on the resist is further increased. The problem of causing unevenness becomes significant. On the other hand, in the large-sized photomask 100 shown in FIG.
  • the reflectance of the surface 120a of the light shielding pattern 120 on the light transmitting substrate 110 side can be reduced to 8% or less.
  • the exposure light that includes light of a plurality of wavelengths such as g-line, h-line, and i-line is transferred to the transfer target. It is possible to remarkably suppress the occurrence of unevenness in the pattern.
  • the light-shielding pattern is a light-shielding pattern provided on the surface of the light-transmitting substrate, and the first low-reflection film, the light-shielding film, and the second low-reflection film are the light-transmitting substrate.
  • the light-transmitting substrate side surface of the light-shielding pattern has a reflectivity with respect to light in the wavelength region of 313 nm to 436 nm of 8% or less.
  • the surface of the light shielding pattern on the light transmitting substrate side has a reflectance with respect to light in the wavelength region of 313 nm to 436 nm of 8% or less. That is, for any light in the wavelength region, the reflectance of the surface of the light shielding pattern on the light transmitting substrate side is 8% or less.
  • the surface of the light-shielding pattern on the light-transmitting substrate side is not particularly limited as long as it has a reflectance with respect to light in the wavelength region of 8% or less, but in particular, the reflectance with respect to light in the wavelength region of 365 nm to 436 nm. Is preferably 5% or less.
  • the intensity of the stray light La shown in FIG. 2 can be reduced to, for example, less than 0.2% of the exposure illuminance. . This is because the intensity of the stray light can be reduced from the level at which the resist layer of the transfer object is exposed to a level that does not completely affect the level.
  • the reflectance with respect to light in the wavelength region of 313 nm to 365 nm is 5% or less. This is because the same effect can be obtained in exposure using exposure light including light in a wider wavelength range. More specifically, not only the current exposure apparatus and resist in which exposure light in the wavelength region of 365 nm to 436 nm is used, but also other exposure apparatus and resist in which exposure light in the wavelength region of 313 nm to 365 nm is used. This is because the same effect can be obtained.
  • a device (Otsuka Electronics MCPD) using a photodiode array as a detector can be used.
  • the surface of the light-shielding pattern opposite to the light-transmitting substrate preferably has a reflectance of 10% or less for light in the wavelength region of 313 nm to 436 nm. That is, for any light in the wavelength region, it is preferable that the reflectance of the surface of the light shielding pattern on the side opposite to the light transmitting substrate is 10% or less.
  • the method for measuring the reflectance of the surface of the light shielding pattern opposite to the light transmissive substrate is the same as the reflectance of the surface of the light shielding pattern on the light transmissive substrate side.
  • the reflectance of the surface 120b on the opposite side of the light-transmitting substrate 110 of the light shielding pattern 120 is 10% or less for any light in the wavelength region of 313 nm to 436 nm. It has become. Therefore, as shown in FIG. 2, a resist layer 220 is formed on a substrate 210 by exposure using exposure light including light in any of the above wavelength regions using a large photomask 100.
  • the exposure light includes the surface 120b of the light shielding pattern 120 on the side opposite to the translucent substrate 110, the interface 212 between the air (not shown) and the resist layer 220, and the resist layer.
  • the resist layer 220 that is originally blocked from exposure light exposure by the edge portion of the light shielding pattern 120 is formed.
  • the intensity of the stray light Lb irradiated can be reduced to, for example, less than 2.0% of the exposure illuminance. Thereby, it is possible to suppress the occurrence of dimensional variation or the like in the pattern transferred to the resist layer 220 at the edge portion.
  • the reflectance with respect to light in the above wavelength region is 10% or less. Reduces the intensity of stray light caused by exposure light reflecting off the surface of the light-shielding pattern opposite to the light-transmitting substrate during exposure using exposure light containing light in any of the wavelength regions By doing so, it is possible to effectively suppress the occurrence of dimensional variation or the like in the pattern transferred to the transfer target.
  • exposure using exposure light including light of a plurality of wavelengths such as g-line, h-line, and i-line, particularly exposure light including j-line, there is a variation in dimensions in the pattern transferred to the transfer target. This is because this can be suppressed more remarkably.
  • the surface of the light shielding pattern opposite to the light transmitting substrate preferably has a reflectance with respect to the light in the wavelength region of 10% or less, and in particular, the reflection with respect to the light in the wavelength region of 365 nm to 436 nm. A rate of 5% or less is preferred.
  • the intensity of the stray light Lb shown in FIG. 2 can be reduced to, for example, less than 1.0% of the exposure illuminance. .
  • the intensity of the stray light is changed from the level of the boundary where the resist layer is exposed to such an extent that the pattern transferred to the resist layer of the transferred object at the edge portion of the light shielding pattern has a dimensional variation.
  • variations can be reduced to a level at which no variation occurs.
  • the reflectance with respect to light in the wavelength region of 313 nm to 365 nm is 5% or less. This is because the same effect can be obtained in exposure using exposure light including light in a wider wavelength range.
  • the first low-reflection film is provided on the light-transmitting substrate side in the laminated structure of the light-shielding pattern, and has a thickness of 313 nm to 436 nm on the surface of the light-shielding pattern on the light-transmitting substrate side. It is a film that realizes the function of reducing the reflectance to light in the wavelength region to 8% or less.
  • the light shielding pattern has the first low reflection film
  • the light transmission of the first low reflection film when light in the wavelength region is irradiated onto the surface of the light shielding pattern on the light transmitting substrate side, the light transmission of the first low reflection film.
  • the light reflected from the surface on the optical substrate side, the light reflected from the internal interface of the first low reflection film, and the light reflected from the boundary between the first low reflection film and the light shielding film are caused by interference.
  • substrate of the said light shielding pattern can be reduced to 8% or less.
  • the film thickness of the first low reflective film it is possible to realize a function of reducing the reflectance of the light shielding pattern on the light transmitting substrate side to the light in the wavelength region to 8% or less. If it is, it will not specifically limit, but the film thickness which falls in the range of 10 nm-50 nm is preferable. This is because if the thickness is too thin, the function of reducing the reflectance decreases, and if the thickness is too thick, it is difficult to process the light shielding pattern with high accuracy.
  • the material of the first low reflection film is not particularly limited as long as it is a material that can reduce the reflectance of the light shielding pattern on the light transmitting substrate side to the light in the wavelength region to 8% or less.
  • chromium oxide (CrO X ) and chromium oxynitride (CrON) are preferable, and chromium oxide (CrO X ) is particularly preferable.
  • the formation method of the first low reflection film examples include a sputtering method, a vacuum deposition method, and an ion plating method. More specifically, for example, a method in which a Cr target is mounted in a vacuum chamber, O 2 , N 2 , CO 2 gas is introduced, and a film is formed by reactive sputtering in a vacuum environment. It is done. In this method, by increasing the O 2 gas ratio as compared with the case of forming a low reflection film in a light shielding pattern of a general binary mask, the surface of the light shielding pattern on the light transmitting substrate side is 313 nm. The reflectance for light in the wavelength region of ⁇ 436 nm is reduced to 8% or less.
  • the second low-reflection film is provided on the opposite side of the light-transmitting substrate in the stacked structure of the light-shielding pattern, and is provided on the opposite side of the light-shielding pattern to the light-transmitting substrate. It is a film that realizes a function of reducing the reflectance of light in the wavelength region of 313 nm to 436 nm on the surface.
  • the light-shielding pattern has the second low-reflection film
  • the second low-reflection film Reflected at the boundary between the second low-reflection film and the light-shielding film, reflected from the surface opposite to the translucent substrate, reflected from the internal interface of the second low-reflection film
  • the second low-reflection film is a film that realizes a function of reducing the reflectance with respect to light in the wavelength region of 313 nm to 436 nm on the surface of the light-shielding pattern opposite to the light-transmitting substrate. Although there is no particular limitation as long as it is present, a film that realizes a function of reducing the reflectance with respect to light in the wavelength region of 313 nm to 436 nm on the opposite surface to 10% or less is preferable.
  • the film thickness of the second low reflection film is not particularly limited as long as it can realize a function of reducing the reflectance of the light in the wavelength region on the surface opposite to the light transmitting substrate of the light shielding pattern.
  • a film thickness in the range of 10 nm to 50 nm is preferable. This is because if the thickness is too thin, the function of reducing the reflectance decreases, and if the thickness is too thick, it is difficult to process the light shielding pattern with high accuracy.
  • the material of the second low reflection film is the same as that of the first low reflection film, description thereof is omitted here.
  • the reflectance of the light shielding pattern on the side opposite to the light transmitting substrate with respect to light in the wavelength region of 313 nm to 436 nm is reduced to 10% or less. Since it is the same as the formation method of a 1st low reflection film, description here is abbreviate
  • the light-shielding film is a film having a light-shielding property provided between the first low-reflection film and the second low-reflection film in the laminated structure of the light-shielding pattern.
  • the film thickness of the light-shielding film is not particularly limited, but a film thickness in the range of 80 nm to 180 nm is preferable. This is because it is difficult to obtain a desired light shielding property if it is too thin, and it is difficult to process the light shielding pattern with high accuracy if it is too thick.
  • the material of the light-shielding film is not particularly limited as long as it has a light-shielding property.
  • chromium (Cr), chromium oxynitride (CrON), chromium nitride (CrN), molybdenum silicide oxide (MoSiO) examples thereof include molybdenum silicide oxynitride (MoSiON), tantalum oxide (TaO), and tantalum silicide oxide (TaSiO).
  • Cr chromium
  • CrON chromium oxynitride
  • CrN chromium nitride
  • MoSiO molybdenum silicide oxide
  • MoSiON molybdenum silicide oxynitride
  • TaO tantalum oxide
  • TaSiO tantalum silicide oxide
  • Method for Forming Light-shielding Film examples include a sputtering method, a vacuum deposition method, and an ion plating method.
  • the time for forming the light-shielding film is extended more than usual. And a method of increasing the number of film forming scans.
  • Light shielding pattern a Optical density (OD)
  • the light shielding pattern preferably has an optical density (OD) of 4.5 or more for light in the wavelength region of 313 nm to 436 nm. That is, for any light in the above wavelength region, an optical density (OD) of 4.5 or more is preferable.
  • an ultraviolet / visible spectrophotometer (Hitachi U-4000) can be used as a method of measuring the optical density (OD) with respect to light in the wavelength region.
  • the optical density (OD) of the light shielding pattern 120 with respect to light in the wavelength region of 313 nm to 436 nm is 4.5 or more. That is, the optical density (OD) of the light shielding pattern 120 is 4.5 or more for any light in the wavelength region. Therefore, as shown in FIG. 2, a resist layer 220 is formed on a substrate 210 by exposure using exposure light including light in any of the above wavelength regions using a large photomask 100.
  • the intensity of the transmitted light Lc through which the exposure light passes through the light shielding pattern 120 can be reduced to, for example, 0.001% or less of the exposure illuminance. Thereby, it is possible to suppress the occurrence of unevenness in the pattern transferred to the resist layer 220.
  • the optical density (OD) is 4.5 or more.
  • the exposure light is reduced in intensity of transmitted light that passes through the light shielding pattern, thereby causing unevenness in the pattern transferred to the transfer target. It is because it can suppress effectively that this occurs.
  • unevenness or the like occurs in the pattern transferred to the transfer object during exposure using exposure light including light of a plurality of wavelengths such as g-line, h-line, and i-line, particularly exposure light including j-line. It is because it can suppress effectively.
  • optical density (OD) of the light shielding pattern in the photomask it is not preferable to increase the optical density (OD) of the light shielding pattern in the photomask from the viewpoint that the light shielding pattern becomes thick and it is difficult to process with high accuracy. This tendency is particularly remarkable in photomasks used in the manufacture of semiconductor integrated circuits.
  • the width of the light shielding pattern is, for example, a width of 0.1 ⁇ m or more and less than 10.0 ⁇ m.
  • the width of the light shielding pattern is preferably a width whose dimensions are controlled on the order of submicrons.
  • the width of the light shielding pattern is defined by the dimension in the short direction of the planar view shape.
  • the width whose dimension is controlled in the submicron order means a width whose dimension is controlled in units of 0.1 ⁇ m, for example, a width of 0.1 ⁇ m or more and less than 1.0 ⁇ m.
  • the overall film thickness of the light shielding pattern is not particularly limited, but is preferably in the range of 100 nm to 250 nm. This is because it is difficult to obtain a desired light shielding property if it is too thin, and it is difficult to process the light shielding pattern with high accuracy if it is too thick.
  • the light-shielding pattern preferably has an optical density (OD) of 4.5 or more with respect to light in the wavelength region and a desired cross-sectional shape.
  • OD optical density
  • a preferable cross-sectional shape of the light shielding pattern will be described.
  • FIG. 3 is an enlarged view showing the region within the broken line frame shown in FIG. 1 with the drawing upside down.
  • the optical density (OD) with respect to light in the wavelength region of 313 nm to 436 nm of the light shielding pattern 120 is 4.5 or more.
  • the inclination angle ⁇ of the side surface 124a of the light shielding film 124 with respect to the light transmissive substrate 110 is not less than 80 degrees and not more than 90 degrees.
  • FIG. 4 is a schematic cross-sectional view showing a region corresponding to FIG. 3 in a conventional large-sized photomask.
  • the inclination angle ⁇ of the side surface 124 a of the light-shielding film 124 with respect to the translucent substrate 110 is less than 80 degrees.
  • the inclination angle ⁇ of the side surface 124a of the light-shielding film 124 with respect to the translucent substrate 110 is not less than 80 degrees and not more than 90 degrees
  • the inclination angle ⁇ is set as shown in FIG. Unlike the case of less than 80 degrees, reflected light of exposure light (stray light) irradiated to the side surface 124a of the light-shielding film 124 from an oblique direction on the light source side at the time of exposure for transferring the pattern to the resist layer of the transfer target.
  • the possibility of being guided to the opening 120c side of the light shielding pattern 120 increases.
  • the inclination angle of the side surface of the light shielding film with respect to the light transmissive substrate is What is 80 degree
  • the inclination angle of the side surface of the light-shielding film with respect to the light-transmitting substrate is the inclination angle of the tangent of the edge on the side of the light-transmitting film on the side surface of the light-shielding film as indicated by ⁇ in FIG. Means.
  • 5 to 7 are schematic cross-sectional views each showing a region corresponding to FIG. 3 in another example of the large photomask of the present disclosure.
  • the light shielding pattern 120 has an optical density (OD) of 4.5 or more for light in the wavelength region of 313 nm to 436 nm.
  • the side surface 124 a of the light shielding film 124 is a plane perpendicular to the translucent substrate 110, and the side surface 122 a of the first low reflection film 122 and the side surface 126 a of the second low reflection film 126. Projecting from the side surface 124 a of the light-shielding film 124 by a length L 1 in a direction parallel to the light-transmitting substrate 110.
  • the light shielding pattern 120 has an optical density (OD) of 4.5 or more for light in the wavelength region of 313 nm to 436 nm.
  • the side surface 124a of the light shielding film 124 is a concave surface composed of a plurality of planes, and the side surface 122a of the first low reflection film 122 and the side surface of the second low reflection film 126.
  • the side surface 124a of the light-shielding film 124 is narrowed by a width W1 in a direction parallel to the translucent substrate 110 from a position closest to the opening 120c to a position farthest from the position.
  • the light shielding pattern 120 has an optical density (OD) of 4.5 or more for light in the wavelength region of 313 nm to 436 nm.
  • the side surface 124a of the light shielding film 124 is a concave curved surface.
  • the side surface 124a of the light shielding film 124 is constricted by a width W2 in a direction parallel to the translucent substrate 110 from a position closest to the opening 120c to a position farthest from the position.
  • the side surface 122 a of the first low-reflection film 122 and the side surface 126 a of the second low-reflection film 126 are transparent to the side surface 124 a of the light-shielding film 124. 110 protrudes in a direction parallel to the surface 110a. For this reason, the exposure light (stray light) irradiated to the side surface 124a of the light-shielding film 124 from the oblique direction on the light source side at the time of exposure for transferring the pattern to the resist layer included in the transfer target is intensified by the first low reflection film 122.
  • the side surface 124a of the light-shielding film 124 is irradiated. Further, the reflected light of the exposure light applied to the side surface 124 a of the light shielding film 124 is applied to the resist layer after the intensity is reduced by the second low reflection film 126. Therefore, the first low-reflection film 122 and the second low-reflection film 126 can suppress the intensity when the resist layer is irradiated with the exposure light that is applied to the side surface 124 a of the light-shielding film 124 from an oblique direction on the light source side.
  • the side surface of the first low-reflection film or the second low-reflection film is used as the light-shielding pattern having an optical density (OD) of 4.5 or more with respect to light in the wavelength region. It is preferable that the side surface of the reflective film protrudes in a direction parallel to the surface of the translucent substrate with respect to the side surface of the light-shielding film.
  • the light shielding pattern thick so that the optical density (OD) is 4.5 or more, the amount of reflected light of the exposure light irradiated on the side surface of the light shielding film from the oblique direction on the light source side can be reduced. This is because, despite the increase, it is possible to suppress the occurrence of unevenness in the pattern transferred to the transfer target due to the influence of the reflected light.
  • the side surface of the first low reflection film or the side surface of the second low reflection film protrudes in a direction parallel to the surface of the translucent substrate with respect to the side surface of the light-shielding film.
  • Any one of the protrusions is not particularly limited, but those protruding both of these side faces are preferable.
  • the side surface of the first low-reflection film or the side surface of the second low-reflection film protrudes in a direction parallel to the surface of the light-transmitting substrate with respect to the side surface of the light-shielding film.
  • the protrusion length as indicated by L1 and L2 in FIG. 6 is 1/2 or more of the film thickness of the light-shielding film. This is because it is possible to effectively suppress the occurrence of unevenness in the pattern transferred to the transfer target due to the influence of the reflected light.
  • the protruding length means that the side surface of the first low reflection film or the side surface of the second low reflection film is the transparent surface from the position farthest from the opening of the light shielding pattern on the concave side surface of the light shielding film. It means the length protruding in the direction parallel to the surface of the optical substrate.
  • the side surface of the first low-reflection film or the side surface of the second low-reflection film is parallel to the surface of the light-transmitting substrate with respect to the side surface of the light-shielding film for the following reasons. It is preferable that it protrudes.
  • a metal film of chromium or the like has a higher polarity than a metal oxide film of chromium oxide or the like, so that foreign matters tend to adhere to it. Therefore, when the light-shielding film is chromium, the side surface of the light-shielding film is parallel to the surface of the translucent substrate with respect to the side surface of the first low-reflection film or the side surface of the second low-reflection film. If protruding in the direction, there is a high possibility that foreign matter will adhere to the light-shielding film, and it may be difficult to remove the foreign matter by subsequent cleaning.
  • the side surface of the first low-reflection film or the side surface of the second low-reflection film is parallel to the surface of the light-transmitting substrate with respect to the side surface of the light-shielding film. It is preferable that the side surface protrudes, and in particular, both side surfaces protrude.
  • the side surface of the first low-reflection film protrudes most, and then the side surface of the second low-reflection film and the side surface of the light-shielding film. It is preferable that the order is.
  • the side surface of the first low-reflection film protrudes most, so the area where the foreign matter comes into contact with the metal oxide film is large. This is because it becomes easy to peel off.
  • At least a side surface of the first low-reflection film protrudes in a direction parallel to the surface of the light-transmitting substrate with respect to a side surface of the light-shielding film, and further,
  • the angle of the side surface with respect to the surface of the translucent substrate is preferably 56 ° or less.
  • FIG. 12 shows a part of an example of such a large-sized photomask.
  • the side surface 122a of the first low-reflection film 122 and the side surface 126a of the second low-reflection film 126 are on the surface 110a of the light-transmitting substrate 110 with respect to the side surface 124a of the light-shielding film 124. It protrudes in the parallel direction.
  • the angle ⁇ formed between the side surface 122a of the first low reflection film 122 and the surface 110a of the translucent substrate 110 is an angle of 56 ° or less.
  • the angle of the side surface of the first low-reflection film with respect to the surface of the light-transmitting substrate is 56 ° or less, the cleaning fluid at the time of cleaning comes into contact even when foreign matter is attached. Since the area to be processed can be increased, cleaning can be performed efficiently, and problems due to the presence of foreign matter after the cleaning process can be prevented.
  • the angle of the side surface of the first low reflective film with respect to the surface of the light transmissive substrate is a position A where the side surface 122a of the first low reflective film 122 and the surface 110a of the light transmissive substrate 110 are in contact with each other. This is an angle obtained by drawing a straight line from the position B where the film thickness of the first low reflection film 122 starts to decrease and measuring the angle between the straight line and the surface 110a.
  • the fact that the side surface 122a of the first low-reflection film 122 protrudes from the side surface 124a of the light-shielding film 124 means that the position B where the film thickness of the first low-reflection film 122 starts to decrease is B. This means that the side surface 124 a of the light-shielding film 124 protrudes in a direction parallel to the surface 110 a of the translucent substrate 110.
  • the angle of the side surface of the first low-reflection film with respect to the translucent substrate surface is preferably 56 ° or less, and more preferably 40 ° or less. This is because cleaning can be performed more efficiently.
  • the one where the said angle is smaller is preferable, it is preferable that it is 20 degrees or more from a viewpoint of manufacture that actual manufacture is difficult.
  • the side surface of the second low-reflection film also protrudes in a direction parallel to the surface of the light-transmitting substrate rather than the side surface of the light-shielding film. This is because adhesion of foreign matter to the side surface of the light-shielding film, which may be difficult to remove the foreign matter by cleaning due to the influence of adhesiveness to the foreign matter, can be reduced.
  • the side surface 124a of the light-shielding film 124 is concave. For this reason, the reflected light of the exposure light (stray light) irradiated to the side surface 124a of the light-shielding film 124 from the oblique direction on the light source side at the time of exposure to transfer the pattern to the resist layer of the transfer target is reflected on the light source side or the light-shielding pattern.
  • the possibility of being guided to the opening 120c side of 120 increases. Therefore, it can suppress that this reflected light is irradiated to the resist layer from which irradiation of exposure light is blocked
  • FIG. Thereby, it is possible to suppress the occurrence of dimensional variation or the like in the pattern transferred to the resist layer at the edge portion.
  • the light shielding pattern having an optical density (OD) of 4.5 or more with respect to light in the wavelength region it is preferable that the side surface of the light shielding film is concave. .
  • the optical density (OD) is 4.5 or more, the amount of reflected light of the exposure light irradiated on the side surface of the light shielding film from the oblique direction on the light source side can be reduced. This is because, despite the increase, it is possible to suppress the occurrence of dimensional variation or the like in the pattern transferred to the transfer target due to the influence of the reflected light.
  • the constriction width of the side surface of the light shielding film as indicated by W1 and W2 in FIGS. 6 and 7 is the film thickness of the light shielding film. What is 1/2 or more is preferable. This is because it is possible to effectively suppress the occurrence of dimensional variation or the like in the pattern transferred to the transfer target due to the influence of the reflected light.
  • the constriction width means a width in a direction parallel to the surface of the translucent substrate from a position closest to the opening of the light shielding pattern on the side surface of the light shielding film to a position farthest from the opening.
  • the boundary between the light-shielding film and the first low-reflection film and the second low-reflection film may be a clear boundary or an unclear boundary.
  • the light-shielding pattern having the clear boundary is preferable in that the characteristics of each film can be easily controlled individually. Further, the light-shielding pattern having the unclear boundary is preferable in that the processed surface becomes smooth and can be easily manufactured.
  • the light-shielding pattern having a clear boundary is formed by individually forming the first low-reflection film, the light-shielding film, and the second low-reflection film using a sputtering apparatus in which gases are replaced. It can be produced.
  • the first low reflection film, the light shielding film, and the second low reflection film are continuously formed without changing the gas of the sputtering apparatus. Can be produced.
  • the formation method of the light shielding pattern for example, a light shielding layer having a laminated structure in which a first low reflection film, a light shielding film, and a second low reflection film are laminated in this order on the surface of synthetic quartz glass.
  • a method of forming a resist pattern having a desired shape on the surface of the light shielding layer and forming the light shielding layer by wet etching using the resist pattern as a mask may be used.
  • the size of the translucent substrate is not particularly limited as long as it can be a photomask having at least one side of 350 mm or more, and is appropriately selected according to the use of the large photomask of the present disclosure. Although it is not particularly limited, it is preferably 330 mm ⁇ 450 mm or more, particularly preferably within a range of 330 mm ⁇ 450 mm to 1700 mm ⁇ 1800 mm.
  • the film thickness of the translucent substrate can be appropriately selected according to the material and use of the large photomask.
  • the film thickness of the translucent substrate is, for example, about 8 mm to 17 mm.
  • the light-transmitting substrate is light-transmitting, and a light-transmitting substrate used for a general large photomask can be used.
  • the translucent substrate include optically polished low expansion glass (aluminoborosilicate glass, borosilicate glass) and synthetic quartz glass.
  • synthetic quartz glass is particularly preferably used. This is because the thermal expansion coefficient is small and it is easy to manufacture a large photomask.
  • the resin-made translucent substrate can also be used.
  • the light transmissive property of the light transmissive substrate is not particularly limited as long as it is the same as that of a light transmissive substrate used for a general large-sized photomask.
  • the light transmittance in a wavelength region of 313 nm to 436 nm is 80%.
  • the above are preferred, and among them, those of 85% or more, particularly 90% or more are preferred. This is because a light-transmitting substrate with higher purity has less scattering of light passing through the material and has a lower refractive index, so that generation of stray light can be suppressed.
  • the large-sized photomask of the present disclosure includes the light-transmitting substrate and the light-shielding pattern, and has a reflectance of 8% or less with respect to light in the wavelength region on the surface of the light-shielding pattern on the light-transmissive substrate side. Although it will not specifically limit if it is a thing, it has a division pattern used for division
  • Divided exposure means that a transfer area is divided into a plurality of exposure areas on a transfer object, each of the plurality of exposure areas is individually exposed using a large photomask, and each of the plurality of exposure areas is exposed to a photomask.
  • FIG. 8 is a schematic plan view illustrating another example of the large photomask of the present disclosure.
  • FIG. 9 is a schematic plan view showing a pattern transfer body manufactured from a transfer target body using the large photomask shown in FIG.
  • FIGS. 10A to 10B are schematic process cross-sectional views showing a part of the manufacturing process of the pattern transfer body shown in FIG.
  • the large photomask 100 is provided on the translucent substrate 110 and the surface 110a of the translucent substrate 110, and the first divided pattern 150a, the second divided pattern 150b, and the third divided different from each other.
  • the first divided pattern 150a, the second divided pattern 150b, and the third divided pattern 150c are the first low reflection film 122, the light shielding film 124, and the second low pattern, respectively, similarly to the light shielding pattern 120 shown in FIG.
  • the reflective film 126 is a light shielding pattern 120 having a stacked structure in which the reflective film 126 is stacked in this order from the light transmitting substrate 110 side.
  • the surface of the first divided pattern 150a, the second divided pattern 150b, and the third divided pattern 150c on the translucent substrate 110 side has a wavelength region of 313 nm to 436 nm, similar to the light shielding pattern 120 shown in FIG.
  • the reflectance with respect to light is 8% or less.
  • a pattern transfer body 200 ′ shown in FIG. 9 uses a large photomask 100 shown in FIG. 8 to form a first divided pattern 150a, a second divided pattern 150b, and a resist layer 220 of the transfer target 200. And each pattern of the 3rd division
  • a light source UV lamp
  • the pattern transfer body 200 ′ When the pattern transfer body 200 ′ is manufactured, first, in the first exposure, the second divided pattern 150b and the third divided pattern 150c are shielded by the exposure shielding plate 300 (illustrated in FIG. 10), so that the resist The exposure light is irradiated to the layer 220 only through the first divided pattern 150a among the first to third divided patterns. Next, in the second to sixth exposures, the third divided pattern 150c and the first divided pattern 150a are shielded by the exposure shielding plate 300, so that the resist layer 220 is exposed to the first to third divided patterns. The exposure light is irradiated only through the second divided pattern 150b.
  • the first division pattern 150a and the second division pattern 150b are shielded by the exposure shielding plate 300, whereby the resist layer 220 is divided into the third division among the first to third division patterns.
  • the exposure light is irradiated only through the pattern 150c. Accordingly, one first resist pattern 220a to which the first divided pattern 150a is transferred, five second resist patterns 220b to which the second divided pattern 150b is transferred, and one to which the third divided pattern 150c is transferred.
  • the third resist pattern 220c is formed so as to be connected in a single direction. As a result, a continuous single resist pattern is formed.
  • the exposure light is transmitted through the second divided pattern 150b (light shielding pattern 120) as in the step shown in FIG.
  • the resist layer 220 in the shielding region (third exposure region) that is originally blocked by the exposure shielding plate 300 from exposure light exposure By reducing the intensity of the stray light La irradiated can be reduced.
  • the stray light intensity is reduced in the same manner as the second exposure to thereby reduce the resist in the region where the stray light La has been irradiated in the second exposure.
  • the intensity of the stray light Lb further irradiated to the layer 220 can be reduced, and the intensity of the stray light La further irradiated to the resist layer 220 in the region where the stray light Lb has been irradiated in the second exposure can be reduced.
  • the exposure light reflects each surface of the light-shielding pattern when each of the plurality of exposure regions of the transfer object is individually exposed using the large-sized photomask in the divided exposure.
  • the intensity of the stray light can be reduced even when multiple exposure due to the stray light occurs in the resist layer. For this reason, it is possible to remarkably suppress the occurrence of unevenness and dimensional variations in the pattern transferred to the transfer target.
  • the large photomask manufacturing method of the present disclosure is not particularly limited as long as the large photomask having the above-described configuration can be manufactured, and is similar to a general large photomask manufacturing method. be able to.
  • a synthetic quartz glass is prepared as a translucent substrate, and a light shielding layer having a laminated structure in which a first low reflection film, a light shielding film, and a second low reflection film are laminated in this order on the surface of the synthetic quartz glass.
  • a mask blank comprising: is prepared.
  • a resist pattern having a desired shape is formed on the surface of the light shielding layer, and the light shielding layer is processed by wet etching using the resist pattern as a mask to form a light shielding pattern from the light shielding layer. Thereby, a large photomask is manufactured.
  • the etchant used for the wet etching is not particularly limited as long as it can accurately process the light shielding layer and does not damage the light transmitting substrate.
  • a dicerium ammonium solution or the like can be used.
  • the large-sized photomask of this indication can be used suitably for the photolithographic method at the time of manufacture of pattern transfer bodies, such as a functional element for display apparatuses used for a display apparatus, for example.
  • Examples of the display device functional element manufactured using the large photomask of the present disclosure include a substrate with metal wiring used for a TFT substrate, a TFT substrate, etc., a color filter, a substrate with a light shielding part used for a color filter, etc. Can be mentioned.
  • a method for manufacturing a pattern transfer body such as a display device functional element using the large photomask of the present disclosure is not particularly limited, and may be the same as a general manufacturing method using a large photomask manufacturing method. it can.
  • a production process comprising preparing an object to be transferred having a resist layer, exposing the resist layer by irradiating exposure light through a large photomask, and developing the resist layer after exposure A method can be mentioned.
  • the resist used for the resist layer may be the same as a general resist, and may be a positive resist or a negative resist.
  • the positive resist include novolac resin, phenol epoxy resin, acrylic resin, polyimide, and cycloolefin. Specific examples include IP3500 (manufactured by TOK), PFI27 (manufactured by Sumitomo Chemical), ZEP7000 (manufactured by ZEON), and positive resist (manufactured by JSR). Of these, positive resists (manufactured by JSR) are preferred. This is because the sensitivity of the present disclosure becomes remarkable due to high sensitivity.
  • examples of the negative resist include acrylic resin.
  • PGMA polyglycidyl methacrylate
  • SAL601 chemically amplified SAL601
  • JSR negative resist
  • the film thickness of the resist layer is not particularly limited, but is, for example, in the range of 10 nm to 10 ⁇ m.
  • the method for forming the resist layer can be a known method, and thus description thereof is omitted here.
  • the transfer object usually has a substrate for forming a resist layer. Moreover, you may have a metal layer etc.
  • the to-be-transferred body it selects suitably according to the kind of functional element for display apparatuses manufactured.
  • the exposure light used in the exposure step is not particularly limited as long as it can react the resist in the resist layer and includes light in any wavelength region of 313 nm to 436 nm.
  • exposure light exposure light containing light of a plurality of wavelengths such as g-line, h-line and i-line is preferable, and exposure light containing j-line is particularly preferable.
  • the energy of the exposure light applied to the resist layer can be increased, and the exposure can be completed in a shorter exposure time. In addition, the occurrence of unevenness in the pattern transferred to the transfer object is significantly suppressed. Because it can.
  • an ultra high pressure mercury lamp ultra high pressure UV lamp
  • the developing method of the resist layer used in the developing step can be a general method and is not particularly limited.
  • As the developing method for example, a method using a developer can be suitably used.
  • Example A1 First, precision-polished synthetic quartz glass (translucent substrate) having a length ⁇ width ⁇ film thickness of 700 mm ⁇ 800 mm ⁇ 8 mm, and a chromium oxide film (CrO x ) (thickness 30 nm) on the surface of the synthetic quartz glass 1 low reflective film), a 85 nm thick chromium film (Cr) (light-shielding film), and a 30 nm thick chromium oxide film (CrO x ) (second low reflective film) in this order.
  • the light shielding layer is synthesized in the order of a chromium oxide film (first low reflection film), a chromium film (light shielding film), and a chromium oxide film (second low reflection film) using a sputtering method. It was formed by forming a film on the surface of quartz glass. At this time, the chromium oxide film (first low-reflection film), the chromium film (light-shielding film), and the chromium oxide film (second low-reflection film) are individually formed using a sputtering apparatus in which gases are replaced. Went to.
  • the chromium oxide film (first low reflection film) and the chromium oxide film (second low reflection film) are mounted with a Cr target in a vacuum chamber, introduced with O 2 , N 2 , and CO 2 gases, and thus in a vacuum environment. Films were formed by reactive sputtering below.
  • the film formation conditions of the chromium oxide film (first low reflection film) were such that the O 2 gas ratio was increased as compared with the film formation conditions of the low reflection film in the light shielding pattern of a general binary mask.
  • the film formation conditions for the chromium oxide film (second low reflection film) were the same as the film formation conditions for the low reflection film in the light shielding pattern of a general binary mask.
  • the film formation conditions of the chromium film (light-shielding film) were the same as the film formation conditions of the chromium film in the light shielding pattern of a general binary mask.
  • a resist pattern having a desired shape is formed on the surface of the light shielding layer, and the light shielding layer is processed by wet etching using the resist pattern as a mask, thereby including 0.1 ⁇ m or more including a light shielding pattern having a width of 3.0 ⁇ m from the light shielding layer.
  • a light shielding pattern having a width of less than 0.0 ⁇ m was formed. Thus, a large photomask was produced.
  • Example A2 First, precision-polished synthetic quartz glass (translucent substrate) having a length ⁇ width ⁇ film thickness of 700 mm ⁇ 800 mm ⁇ 8 mm, a chromium oxide film (first low reflection film), a chromium film (light-shielding film), and A mask blank having a 180 nm-thickness light-shielding layer having a laminated structure in which a chromium oxide film (second low reflection film) is laminated on the surface of the synthetic quartz glass in this order was produced.
  • the light shielding layer is formed by using a sputtering method in the order of a chromium oxide film (first low reflection film), a chromium film (light shielding film), and a chromium oxide film (second low reflection film). It was formed by forming a film on the surface of synthetic quartz glass. At this time, the chromium oxide film (first low reflection film), the chromium film, and the chromium oxide film (second low reflection film) were continuously formed without changing the gas of the sputtering apparatus.
  • the chromium oxide film (first low reflection film) and the chromium oxide film (second low reflection film) are mounted with a Cr target in a vacuum chamber, introduced with O 2 , N 2 , and CO 2 gases, and thus in a vacuum environment. Films were formed by reactive sputtering below.
  • the film formation conditions of the chromium oxide film (first low reflection film) and the chromium oxide film (second low reflection film) are a ratio of O 2 gas than the film formation conditions of the low reflection film in the light shielding pattern of a general binary mask. Was an increased condition.
  • the film formation conditions of the chromium film (light-shielding film) were the same as the film formation conditions of the chromium film in the light shielding pattern of a general binary mask.
  • a resist pattern having a desired shape is formed on the surface of the light shielding layer, and the light shielding layer is processed by wet etching using the resist pattern as a mask, thereby including 0.1 ⁇ m or more including a light shielding pattern having a width of 3.0 ⁇ m from the light shielding layer.
  • a light shielding pattern having a width of less than 0.0 ⁇ m was formed. Thus, a large photomask was produced.
  • Example A3 First, precision-polished synthetic quartz glass (translucent substrate) having a length ⁇ width ⁇ film thickness of 700 mm ⁇ 800 mm ⁇ 8 mm, and a chromium oxide film (first low-reflection film) having a thickness of 30 nm on the surface of the synthetic quartz glass And a light-shielding layer having a laminated structure in which a chromium film (light-shielding film) having a thickness of 110 nm and a chromium oxide film (second low-reflection film) having a thickness of 30 nm are laminated in this order. did.
  • the light shielding layer is synthesized in the order of a chromium oxide film (first low reflection film), a chromium film (light shielding film), and a chromium oxide film (second low reflection film) using a sputtering method. It was formed by forming a film on the surface of quartz glass. At this time, the chromium oxide film (first low-reflection film), the chromium film (light-shielding film), and the chromium oxide film (second low-reflection film) are individually formed using a sputtering apparatus in which gases are replaced. Went to.
  • the chromium oxide film (first low reflection film) and the chromium oxide film (second low reflection film) are mounted with a Cr target in a vacuum chamber, introduced with O 2 , N 2 , and CO 2 gases, and thus in a vacuum environment. Films were formed by reactive sputtering below.
  • the film formation conditions of the chromium oxide film (first low reflection film) and the chromium oxide film (second low reflection film) are a ratio of O 2 gas than the film formation conditions of the low reflection film in the light shielding pattern of a general binary mask.
  • the film formation conditions of the chromium film (light-shielding film) were set such that the film formation time was longer than the film formation conditions of the chromium film in the light shielding pattern of a general binary mask.
  • a resist pattern having a desired shape is formed on the surface of the light shielding layer, and the light shielding layer is processed by wet etching using the resist pattern as a mask, thereby including 0.1 ⁇ m or more including a light shielding pattern having a width of 3.0 ⁇ m from the light shielding layer.
  • a light shielding pattern having a width of less than 0.0 ⁇ m was formed. Thus, a large photomask was produced.
  • the light shielding layer was formed by forming a film on the surface of the synthetic quartz glass in the order of a chromium film (light shielding film) and a chromium oxide film (low reflection film) by using a sputtering method.
  • the chromium film (light-shielding film) and the chromium oxide film (low reflection film) were individually formed using a sputtering apparatus in which the gases were changed.
  • the chromium oxide film (low reflection film) was formed by reactive sputtering in a vacuum environment with a Cr target mounted in a vacuum chamber, O 2 , N 2 , and CO 2 gas introduced.
  • the film formation conditions of the chromium oxide film were the same as the film formation conditions of the low reflection film in the light shielding pattern of a general binary mask. Furthermore, the film forming conditions of the chromium film were the same as the film forming conditions of the chromium film in the light shielding pattern of a general binary mask.
  • a resist pattern having a desired shape is formed on the surface of the light shielding layer, and the light shielding layer is processed by wet etching using the resist pattern as a mask, thereby including 0.1 ⁇ m or more including a light shielding pattern having a width of 3.0 ⁇ m from the light shielding layer.
  • a light shielding pattern having a width of less than 0.0 ⁇ m was formed. Thus, a large photomask was produced.
  • the Cr content continuously changes, the boundary between the chromium oxide film (first low reflection film) and the chromium film (light shielding film), and the chromium film ( The boundary between the light-shielding film) and the chromium oxide film (second low reflection film) was unclear. Further, at the boundary of the light shielding pattern in the comparative example, the Cr content changed discontinuously, and the boundary between the chromium film (light shielding film) and the chromium oxide film (low reflection film) became clear.
  • the back surface reflectance and the front surface reflectance were measured every 1 nm in the above wavelength region using a spectroscopic analyzer (Otsuka Electronics MCPD3000).
  • the optical density (OD) was measured every 1 nm in the above wavelength region using an ultraviolet / visible spectrophotometer (Hitachi U-4000).
  • Table 3 shows the measurement results of g-line (wavelength 436 nm), h-line (wavelength 405 nm), i-line (wavelength 365 nm), and j-line (wavelength 313 nm).
  • Table 1 summarizes the measurement conditions of the spectroscopic analyzer (Otsuka Electronics MCPD3000), and Table 2 summarizes the measurement conditions of the ultraviolet / visible spectrophotometer (Hitachi U-4000).
  • Resist Pattern Properties A resist layer with a film thickness of 2.5 ⁇ m formed on a glass substrate for the purpose of forming a resist pattern of a desired shape using the large photomasks of Examples A1 to A3 and Comparative Example A An exposure stepper type (reduced projection type) proxy exposure was performed on (manufactured by JSR) under the following exposure conditions.
  • Exposure gap 150 ⁇ m
  • Exposure light Exposure light exposure including g-line, h-line, i-line, and j-line: 200 mJ / cm 2
  • the film thickness variation with respect to the normal portion of the uneven portion of the resist pattern (hereinafter referred to as “uneven portion film thickness variation”). Yes.) Specifically, the ratio [%] of uneven portion film thickness variation of Examples A1 to A3 when the uneven portion film thickness variation of Comparative Example A was set to 100% was measured. The results are shown in Table 3 below.
  • the back surface reflectance is 8% or less for any of g-line, h-line, i-line, and j-line, and is not shown in Table 3 above. However, similar results were obtained for light of other wavelengths in the above wavelength region.
  • the surface reflectance is 10% or less for any of g-line, h-line, i-line, and j-line. Although not shown, similar results were obtained for light of other wavelengths in the above wavelength region.
  • the optical density (OD) is 4.5 or more for any of g-line, h-line, i-line, and j-line.
  • Example A3 As shown in Table 3 above, in Examples A1 to A3, variation in the uneven portion film thickness could be suppressed as compared with the comparative example. Moreover, in Example A2 and A3, the uneven
  • Example B1 A large photomask was prepared in the same manner as in Example A3. The created large photomask was cut within 20 mm (h) ⁇ 30 mm (w) ⁇ 8 mm (d) using a glass cutter. The cut surface was sputtered with platinum (20 mA ⁇ 12 seconds) and observed with an electron microscope.
  • the electron microscope was a scanning electron microscope (JEOL Co., Ltd., JSM-6700F) with an acceleration voltage of 5.0 kV, an inclination of 0 °, a mode of SEI (downward detection of secondary electrons), and a working distance of 3 .2 mm to 3.3 mm (fine adjustment according to the height of the sample), the number of integration was one (Fine View mode), and the observation magnification was ⁇ 100K.
  • the measurement location was a light shielding pattern portion having a width of 3.0 ⁇ m. As a result of the measurement, it was found that the angle of the side surface of the first low reflection film with respect to the surface of the translucent substrate was 80 °.
  • this angle is determined by the position where the side surface of the first low-reflection film and the surface of the light-transmitting substrate are in contact with each other, and the position where the film thickness of the first low-reflection film starts to decrease. Is an angle obtained by drawing a straight line and measuring the angle between the straight line and the surface.
  • Example B1 With respect to such a large photomask of Example B1, pure water cleaning is performed for 300 seconds and then dried, and the number of foreign matters after cleaning is determined by the sensitivity with which a foreign matter having a size of 1 ⁇ m or more can be detected by reflection inspection of an appearance inspection machine. It was measured.
  • This measured value is a value obtained by measuring an area of 690 mm ⁇ 790 mm excluding the end 5 mm of the four sides of the glass substrate.
  • the measured values are shown in Table 4 as a ratio when the value according to Comparative Example B described later is 100.
  • Examples B2 to B5 The etching conditions of Example B1 were changed in the direction of extending the etching time, and the angle of the side surface of the first low-reflection film with respect to the surface of the translucent substrate was changed. A photomask was prepared. The angle was measured in the same manner as in Example B1.
  • Comparative Example B A large photomask was prepared in the same manner as in Comparative Example A above.
  • the angle of the side surface of the first low-reflection film with respect to the surface of the light-transmitting substrate was measured in the same manner as in Example B1.
  • the obtained large sized photomask was wash

Abstract

L'invention concerne un photomasque de grande taille comprenant un substrat translucide et un motif de protection contre la lumière disposé sur la surface du substrat translucide, le photomasque de grande taille étant caractérisé en ce que : le motif de protection contre la lumière a une structure stratifiée dans laquelle sont stratifiés à partir du côté du substrat translucide une première couche à faible réflexion, un film de protection contre la lumière et une seconde couche à faible réflexion, et ce dans l'ordre indiqué ; et la surface située sur le côté substrat translucide du motif de protection contre la lumière possède une réflectance à la lumière se trouvant dans une région de longueur d'onde de 313 à 436 nm de 8 % ou moins.
PCT/JP2019/010647 2018-03-15 2019-03-14 Photomasque de grande taille WO2019177116A1 (fr)

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CN201980032507.6A CN112119352A (zh) 2018-03-15 2019-03-14 大型光掩模
JP2020506656A JP7420065B2 (ja) 2018-03-15 2019-03-14 大型フォトマスク
KR1020207029308A KR102653366B1 (ko) 2018-03-15 2019-03-14 대형 포토마스크
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