WO2022239752A1 - 反射型マスクブランクおよびその製造方法、ならびに該マスクブランク用の反射層付き基板 - Google Patents

反射型マスクブランクおよびその製造方法、ならびに該マスクブランク用の反射層付き基板 Download PDF

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Publication number
WO2022239752A1
WO2022239752A1 PCT/JP2022/019739 JP2022019739W WO2022239752A1 WO 2022239752 A1 WO2022239752 A1 WO 2022239752A1 JP 2022019739 W JP2022019739 W JP 2022019739W WO 2022239752 A1 WO2022239752 A1 WO 2022239752A1
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Prior art keywords
layer
reflective
substrate
metal
mask blank
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English (en)
French (fr)
Japanese (ja)
Inventor
竜輔 大石
貴大 菊池
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AGC Inc
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Asahi Glass Co Ltd
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Priority to KR1020237038710A priority Critical patent/KR20240007154A/ko
Priority to JP2023521195A priority patent/JPWO2022239752A1/ja
Publication of WO2022239752A1 publication Critical patent/WO2022239752A1/ja
Priority to US18/495,839 priority patent/US20240053671A1/en
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/3435—Applying energy to the substrate during sputtering
    • C23C14/3442—Applying energy to the substrate during sputtering using an ion beam
    • 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
    • G03F1/22—Masks or mask blanks for imaging by radiation of 100nm or shorter wavelength, e.g. X-ray masks, extreme ultraviolet [EUV] masks; Preparation thereof
    • G03F1/24—Reflection masks; Preparation thereof
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/0021—Reactive sputtering or evaporation
    • C23C14/0036—Reactive sputtering
    • C23C14/0057—Reactive sputtering using reactive gases other than O2, H2O, N2, NH3 or CH4
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/46—Sputtering by ion beam produced by an external ion source

Definitions

  • the present invention relates to a reflective mask blank, a manufacturing method thereof, and a substrate with a reflective layer for the mask blank.
  • EUV Ultra Violet
  • EUV light with a shorter wavelength than ArF excimer laser light is used as the light source for exposure.
  • EUV light refers to light having a wavelength in the soft X-ray region or vacuum ultraviolet region, and specifically, light having a wavelength of approximately 0.2 to 100 nm. EUV light with a wavelength of about 13.5 nm, for example, is used as the EUV light.
  • EUV light is easily absorbed by all substances, so the refractive optics used in conventional exposure technology cannot be used. Therefore, in EUV lithography, a reflective optical system such as a reflective mask and a mirror is used. In EUV lithography, a reflective mask is used as a transfer mask.
  • a mask blank is a pre-patterned laminate used in photomask manufacturing.
  • a reflective mask blank has a structure in which a reflective layer that reflects EUV light and an absorption layer that absorbs EUV light are formed in this order on a substrate made of glass or the like.
  • As the reflective layer by alternately laminating a low refractive index layer that has a low refractive index for EUV light and a high refractive index layer that has a high refractive index for EUV light, EUV light can be reflected on the layer surface.
  • a reflective multi-layer film having an enhanced light reflectance upon irradiation is usually used.
  • a molybdenum (Mo) layer is usually used as the low refractive index layer of the reflective multilayer film, and a silicon (Si) layer is usually used as the high refractive index layer.
  • a material having a high absorption coefficient for EUV light specifically a material containing chromium (Cr) or tantalum (Ta) as a main component, for example, is used.
  • the sputtering method can be used to form a reflective multilayer film and an absorption layer. It is preferably used for a reason.
  • an ion beam sputtering method is preferably used for forming the high refractive index layer and the low refractive index layer that constitute the reflective multilayer film (Patent Document 1).
  • the sputtering method is a film forming method in which charged particles impact the surface of a sputtering target, eject the sputtered particles from the target, and deposit the sputtered particles on a substrate placed facing the target to form a thin film.
  • a sputtering gas is introduced into the ion source, and thermal electrons generated from the filament inside the ion source collide with the introduced gas to ionize and generate plasma. Let By applying an electric field to the grid electrode, this plasma is extracted as an ion beam, accelerated, and made to collide with a target for sputtering.
  • the extracted ion beam travels straight with a constant diffusion angle. Therefore, there is a problem that the ion beam collides with peripheral members other than the target.
  • the collision of the ion beam advances the sputtering of the target peripheral member, for example, the anti-adhesion shield, generating sputtered particles.
  • contamination hereinafter, sometimes referred to as "contamination derived from the target peripheral member" in the specification of the present application
  • the refractive index of these layers changes. This may reduce the reflectance.
  • the peak reflectance of light in the EUV wavelength region on the surface of the reflective multilayer film is locally low at the site where the contamination occurs. As a result, the intensity of the peak reflectance of light in the EUV wavelength region is reduced on the surface of the reflective multilayer film.
  • the resist on the wafer is irradiated when EUV lithography is performed using a reflective mask made from a reflective mask blank. Insufficient EUV exposure may occur. This results in insufficient patterning within the exposure field, which is a factor that hinders high-precision patterning.
  • An object of the present invention is to provide a reflective mask blank in which a reflective multilayer film has excellent reflectance characteristics, a method for manufacturing the same, and a substrate with a reflective layer for the mask blank.
  • Ions generated by using a process gas containing at least one inert gas selected from He, Ne, Ar, Kr, Xe, Rn and N2 as an ion source and applying a voltage to the grid is accelerated and the ions are made to collide with a target to perform sputtering, forming a reflective multilayer film on a substrate using an ion beam sputtering apparatus, comprising:
  • the product of the effective area (cm 2 ) of the grid and the flow rate (sccm) of the process gas supplied to the ion beam sputtering apparatus during film formation is 3600 (cm 2 ⁇ sccm) or less.
  • a method for manufacturing a reflective mask blank [2] The method for producing a reflective mask blank according to [1], wherein in the ion beam sputtering apparatus, an anti-adhesion shield is arranged so as to cover the target. [3] The constituent material of the anti-adhesion shield is at least one selected from the group consisting of Al, Fe, Cr, Ni, Y, Cu, Mn, Zn, Si, Mg, V, Sn, Mo and Zr. The method for producing a reflective mask blank according to [2], containing the element.
  • the product of the effective area (cm 2 ) of the grid and the flow rate (sccm) of the process gas supplied to the ion beam sputtering apparatus during film formation is 1000 (cm 2 ⁇ sccm) or more.
  • the reflective layer is a reflective multilayer film formed by alternately laminating a low refractive index layer and a high refractive index layer multiple times,
  • the metal atom having the highest content in the low refractive index layer is defined as metal X, the metal constituting the substrate, the metal constituting the low refractive index layer, and the high refractive index layer.
  • the metal Y is a metal other than the metal constituting the component of the protective layer
  • the metal Y with respect to the peak attributed to the metal X A substrate with a reflective layer, wherein the intensity ratio of the peak attributed to metal Y (the intensity of the peak attributed to metal Y/the intensity of the peak attributed to metal X) is 0.0060 or less.
  • the metal Y is at least one element selected from the group consisting of Al, Fe, Cr, Ni, Y, Cu, Mn, Zn, Si, Mg, V, Sn, Mo and Zr, [ 6], the substrate with a reflective layer.
  • the metal Y is at least one element selected from the group consisting of Al, Fe, Cr, Ni, Y, Cu, Mn, Zn, Si, Mg, V, Sn and Zr, [8] The substrate with a reflective layer according to .
  • a reflective mask blank in which an absorption layer for absorbing EUV light is formed on the protective layer of the substrate with a reflective layer according to any one of [6] to [10].
  • the reflective mask blank according to [11] wherein a low reflection layer for inspection light used for mask pattern inspection is formed on the absorption layer.
  • the present invention can provide a reflective mask blank in which the reflective multilayer film has excellent reflectance characteristics, a method for manufacturing the same, and a substrate with a reflective layer for the mask blank.
  • FIG. 1 is a schematic cross-sectional view showing one embodiment of the substrate with a reflective layer of the present invention.
  • FIG. 2 is a schematic cross-sectional view showing one embodiment of the reflective mask blank of the present invention.
  • the method for manufacturing a reflective mask blank of the present embodiment uses, as an ion source, a process gas containing at least one inert gas selected from He, Ne, Ar, Kr, Xe, Rn and N2 , It includes a procedure for forming a reflective multilayer film on a substrate using an ion beam sputtering apparatus that accelerates ions generated by applying a voltage to a grid and causes the ions to collide with a target for sputtering.
  • the ion beam sputtering apparatus described above is used to form a low refractive index layer having a low refractive index for EUV light and a high refractive index layer for EUV light on the substrate.
  • a reflective multi-layer film is formed by alternately laminating high refractive index layers.
  • the inventors of the present application have obtained the following knowledge regarding the occurrence of contamination originating from members surrounding the target in the reflective multilayer film formed on the substrate using the ion beam sputtering apparatus described above.
  • the inventors of the present application have found that the product of the effective area S (cm 2 ) of the grid and the flow rate F (sccm) of the process gas supplied to the ion beam sputtering apparatus during film formation (S ⁇ F ) to a predetermined value or less, the occurrence of contamination in the reflective multilayer film originating from members surrounding the target is suppressed, and the reflectance characteristics of the reflective multilayer film are improved.
  • the inventors have found that the intensity of the peak reflectance of light in the EUV wavelength region on the surface of the reflective multilayer film is improved by the above.
  • the manufacturing method of the reflective mask blank of the present embodiment is based on the product ( S ⁇ F) is 3600 (cm 2 ⁇ sccm) or less.
  • the product (S ⁇ F) of the effective area S of the grid and the flow rate F of the process gas during film formation satisfies the above range, the occurrence of contamination originating from members around the target in the reflective multilayer film is suppressed. This improves the reflectance characteristics of the reflective multilayer film, specifically, improves the in-plane uniformity of the peak reflectance of light in the EUV wavelength region on the surface of the reflective multilayer film.
  • the product (S ⁇ F) of the effective area S (cm 2 ) of the grid and the flow rate F (sccm) of the process gas during film formation is 3000 (cm 2 ). ⁇ sccm) or less, and more preferably 2500 (cm 2 ⁇ sccm) or less.
  • the product (S ⁇ F) of the effective area S (cm 2 ) of the grid and the flow rate F (sccm) of the process gas during film formation is 1000 (cm 2 ). ⁇ sccm) or more, more preferably 1500 (cm 2 ⁇ sccm) or more, and even more preferably 1800 (cm 2 ⁇ sccm) or more. If the product (S ⁇ F) of the effective area S of the grid and the flow rate F of the process gas during film formation is 1000 (cm 2 ⁇ sccm) or more, electrons are generated by gas collision in the ion beam sputtering apparatus. This is excellent in that the ion beam is sufficiently neutralized.
  • the effective area S (cm 2 ) of the grid refers to the area of the portion of the grid provided with the lattice-shaped openings.
  • r is the radius (cm) of the portion of the grid provided with the grid-like openings
  • the nominal diameter (cm) of the portion of the grid provided with the grid-like openings is 1. /2 times.
  • the shape of the part of the grid where the grid-shaped openings are provided is often circular. Among them, the equivalent circle diameter of the portion where the grid-shaped opening is provided is obtained, and r is obtained therefrom.
  • the effective area S of the grid is preferably 200 cm 2 or less.
  • the effective area S of the grid is more preferably 190 cm 2 or less.
  • the effective area S of the grid is preferably 100 cm 2 or more. If the effective area S of the grid is 100 cm 2 or more, the productivity of the reflective mask blank is excellent. More preferably, the effective area S of the grid is 110 cm 2 or more.
  • the flow rate F of the process gas supplied to the ion beam sputtering apparatus during film formation is preferably 18 sccm or less.
  • the flow rate F of the process gas during film formation is preferably 5 sccm or more. If the flow rate F of the process gas during film formation is 5 sccm or more, the discharge stability is excellent.
  • the process gas supplied to the ion beam sputtering apparatus may contain only one of He, Ne, Ar, Kr, Xe, Rn and N2 , Two or more types may be included.
  • the process gas supplied to the ion beam sputtering apparatus preferably contains Ar from the viewpoint of economic efficiency and ease of discharge.
  • ion beam sputtering may be performed by selecting a sputtering target according to the reflective multilayer film to be formed.
  • the reflective multilayer film is a Mo/Si reflective multilayer film
  • a Mo target is used as the target, and at least one selected from He, Ne, Ar, Kr, Xe, Rn and N as the ion source.
  • a process gas containing an inert gas a voltage is applied to the grid to accelerate the ions generated, and the ions are made to collide with a Mo target to perform sputtering, thereby forming a Mo layer as a low refractive index layer.
  • a process gas containing at least one inert gas selected from He, Ne, Ar, Kr, Xe, Rn and N2 as the ion source, and grid A voltage is applied to accelerate the generated ions, the ions are made to collide with the Si target, and sputtering is performed to form a Si layer as a high refractive index layer.
  • This procedure is alternately repeated to form a reflective multilayer film in which Mo layers and Si layers are alternately laminated a predetermined number of times on the substrate.
  • the ion beam sputtering conditions for forming the reflective multilayer film other than the effective area S of the grid and the flow rate F of the process gas during film formation are the reflective multilayer film to be formed. Select accordingly.
  • the beam voltage is preferably 100-1500V, more preferably 150-1200V, even more preferably 200-1000V.
  • the pressure in the chamber is preferably 1.0 Pa or less, more preferably 1.0 ⁇ 10 ⁇ 1 Pa or less, even more preferably 8.0 ⁇ 10 ⁇ 2 Pa or less, particularly 6.0 ⁇ 10 ⁇ 2 Pa or less. preferable.
  • an anti-adhesion shield is arranged so as to cover the target in order to prevent foreign matter from adhering to the target.
  • the target and the anti-adhesion shield placed around the target may be rotated, and Al, which is lighter than SUS (stainless steel), may be used in consideration of the load on the servomotor.
  • the sputtering apparatus may be provided with an anti-adhesion plate to prevent deposition of a film in the chamber, but the anti-adhesion plate and the anti-adhesion shield are generally different in material and pretreatment.
  • the constituent material of the anti-adhesion shield is not particularly limited, but at least one selected from the group consisting of Al, Fe, Cr, Ni, Y, Cu, Mn, Zn, Si, Mg, V, Sn, Mo and Zr. It is preferable to contain an element for reasons of workability and material stability during use, and it is more preferable to contain Al.
  • the constituent material of the anti-adhesion shield may contain two or more of the above elements.
  • the procedure for forming the reflective multilayer film on the substrate there is no particular limitation other than the procedure for forming the reflective multilayer film on the substrate.
  • the protective layer is formed using a well-known film forming method such as magnetron sputtering or ion beam sputtering.
  • a Ru layer is formed as a protective layer using the ion beam sputtering apparatus described above, a Ru target is used as the target, and He, Ne, Ar, Kr, Xe, Rn and N are used as the ion source.
  • a process gas containing at least one selected inert gas a voltage is applied to the grid to accelerate generated ions, and the ions are made to collide with a Ru target for sputtering to form a Ru layer. .
  • the effective area of the grid S (cm 2 ), the flow rate F (sccm) of the process gas during film formation, the effective area S (cm 2 ) of the grid and the flow rate F (of the process gas during film formation) sccm) and the product (S ⁇ F) preferably satisfies the conditions described for the reflective multilayer film.
  • the beam voltage and the preferred range of pressure in the chamber are the same as those described for the reflective multilayer film.
  • the absorption layer In the procedure for forming the absorption layer, it is formed using a dry film forming method such as a magnetron sputtering method or a sputtering method such as an ion beam sputtering method.
  • a dry film forming method such as a magnetron sputtering method or a sputtering method such as an ion beam sputtering method.
  • Ta target Sputtering gas Mixed gas of Ar, N2 and H2 (H2 gas concentration 1-30 vol %, N2 gas concentration 5-75 vol%, Ar gas concentration 10-94 vol%, gas pressure 0.5 ⁇ 10 -1 Pa to 1.0 Pa)
  • Input power 300-2000W
  • a dry film-forming method such as magnetron sputtering or ion beam sputtering is used.
  • Ta target Sputtering gas Mixed gas of Ar, O 2 and N 2 (O 2 gas concentration 5-80 vol%, N 2 gas concentration 5-75 vol%, Ar gas concentration 5-90 vol%, gas pressure 1.0 ⁇ 10 -1 Pa to 50 ⁇ 10 -1 Pa)
  • Input power 30 to 1000W
  • FIG. 1 is a schematic cross-sectional view showing one embodiment of the substrate with a reflective layer of the present invention.
  • a substrate 1 with a reflective layer shown in FIG. 1 has a reflective layer 12 and a protective layer 13 for the reflective layer 12 formed on a substrate 11 in this order.
  • the reflective layer 12 is a reflective multilayer film formed by alternately stacking low refractive index layers and high refractive index layers multiple times.
  • the substrate with a reflective layer of the present invention is manufactured by the method of manufacturing a reflective mask blank of the present invention.
  • the metal atom having the highest content in the low refractive index layer is the metal X, the metal constituting the substrate 11, the metal constituting the low refractive index layer, and the high refractive index layer.
  • metal Y a metal other than the metal constituting the index layer and the metal constituting the protective layer 13
  • XRF X-ray fluorescence analysis
  • the metal atom having the highest content in the low refractive index layer is the metal X.
  • a molybdenum (Mo) layer is usually used as the low refractive index layer of the reflective multilayer film, and a silicon (Si) layer is usually used as the high refractive index layer. Therefore, the metal atom with the highest content in the high refractive index layer is generally Si.
  • SiO 2 —TiO 2 -based glass is usually used for the substrate and contains Si.
  • Mo is generally the metal atom with the highest content in the low refractive index layer.
  • the substrate underlying the reflective multilayer film generally does not contain Mo. Therefore, when measuring the substrate with the reflective layer by XRF, it is easy to identify the peak attributed to Mo in the reflective multilayer film.
  • any one of these metal atoms is defined as metal X.
  • a metal that constitutes a component of the substrate 11 refers to a metal that is intentionally blended as a component of the substrate 11 .
  • Metals mixed into the substrate 11 as impurities are not included. The same applies to the metal forming the component of the low refractive index layer, the metal forming the component of the high refractive index layer, and the component constituting the protective layer. Therefore, representative examples of the metal Y are metals that form contamination derived from target peripheral members in the reflective multilayer film. , Mo, and Zr.
  • Intensity ratio of the peak attributed to metal Y to the peak attributed to metal X when measuring the substrate with a reflective layer by XRF is 0.0060 or less
  • the amount of metal Y, which forms contamination derived from members surrounding the target in the reflective multilayer film, is extremely small relative to the metal X constituting the low refractive index layer of the reflective multilayer film. Therefore, a decrease in intensity of the peak reflectance of light in the EUV wavelength region on the surface of the reflective multilayer film is suppressed.
  • the intensity ratio of the peak attributed to metal Y to the peak attributed to metal X is preferably 0.0055 or less, and 0.0055 or less. 0050 or less is more preferable.
  • the intensity ratio of the peak attributed to metal Y to the peak attributed to metal X is preferably 0.00001 or more.
  • the peak intensity attributed to metal Y is the maximum value among the peak intensities attributed to these elements.
  • the substrate with a reflective layer of this embodiment will be further described.
  • the substrate 11 satisfies the properties as a substrate for EUV mask blanks. Therefore, the substrate 11 preferably has a low thermal expansion coefficient (specifically, a thermal expansion coefficient of 0 ⁇ 0.05 ⁇ 10 ⁇ 7 /° C. at 20° C., more preferably 0 ⁇ 0.03 ⁇ 10 ⁇ 7 /° C.). ), and is excellent in smoothness, flatness, and resistance to cleaning solutions used for cleaning mask blanks or photomasks after pattern formation.
  • glass having a low coefficient of thermal expansion such as SiO 2 —TiO 2 -based glass, is specifically used.
  • Substrates such as metal can also be used.
  • the substrate 11 preferably has a smooth surface with a surface roughness (rms) of 0.15 nm or less and a flatness of 100 nm or less, because high reflectance and transfer accuracy can be obtained in the photomask after pattern formation.
  • rms surface roughness
  • the size, thickness, etc. of the substrate 11 are appropriately determined according to the design values of the mask. It is preferable that the surface of the substrate 11 on which the reflective multilayer film is formed has no defects. However, even if defects are present, the concave defects and/or the convex defects should not cause topological defects. Specifically, the depth of the concave defect and the height of the convex defect are preferably 2 nm or less, and the half width of these concave and convex defects is preferably 60 nm or less.
  • the half-value width of the concave defect indicates the width of the concave defect at a half depth position.
  • the half-value width of a convex defect refers to the width of the convex defect at a half height position.
  • the reflective multilayer film achieves high EUV light reflectance by alternately laminating high refractive index layers and low refractive index layers multiple times.
  • Si is widely used for high refractive index layers
  • Mo is widely used for low refractive index layers. That is, the Mo/Si reflective multilayer film is the most common.
  • the reflective multilayer film is not particularly limited as long as it has the desired properties as the reflective layer of the reflective mask blank.
  • a property particularly required for the reflective multilayer film is high EUV light reflectance.
  • the peak reflectance of light in the EUV wavelength region that is, the light reflectance in the vicinity of a wavelength of 13.5 nm
  • the maximum value, hereinafter referred to as "EUV light peak reflectance" in the specification of the present application is preferably 60% or more, more preferably 65% or more.
  • the peak reflectance of EUV light is preferably 60% or more, more preferably 65% or more.
  • each layer constituting the reflective multilayer film and the number of layer repeating units can be appropriately selected according to the film material used and the EUV light reflectance required for the reflective layer.
  • the reflective multilayer film has a Mo layer with a thickness of 2.3 nm ⁇ 0.1 nm, A Si layer having a film thickness of 4.5 nm ⁇ 0.1 nm may be laminated so that the number of repeating units is 30 to 60.
  • the uppermost layer of the reflective multilayer film be a layer of a material that is difficult to oxidize.
  • the layer of material resistant to oxidation functions as a cap layer for the reflective multilayer.
  • a specific example of a layer of a material that is resistant to oxidation that functions as a cap layer is a Si layer.
  • the reflective multilayer film is a Mo/Si reflective multilayer film
  • the uppermost layer functions as a cap layer by using a Si layer as the uppermost layer. In that case, the film thickness of the cap layer is preferably 11 ⁇ 2 nm.
  • the protective layer 13 is provided for the purpose of protecting the reflective multilayer film from being damaged by the etching process when patterning the absorbing layer 14 by an etching process, typically a dry etching process. Therefore, as the material for the protective layer, a material is selected which is less affected by the etching process of the absorption layer 14, that is, a material which has a lower etching rate than the absorption layer 14 and which is less likely to be damaged by this etching process. In order to satisfy the above characteristics, the protective layer 13 preferably contains Ru.
  • the film thickness of the protective layer 13 is preferably 1 to 60 nm, more preferably 1 to 40 nm.
  • FIG. 2 is a schematic cross-sectional view showing one embodiment of the reflective mask blank of the present invention.
  • a reflective mask blank 10 shown in FIG. 2 has a reflective layer 12, a protective layer 13, and an absorbing layer 14 formed on a substrate 11 in this order.
  • a reflective mask blank 10 shown in FIG. 2 is formed by forming an absorption layer 14 on a protective layer 13 of a substrate 1 with a reflective layer shown in FIG.
  • a characteristic particularly required for the absorption layer 14 is an extremely low EUV light reflectance.
  • the peak reflectance of EUV light when the surface of the absorption layer 14 is irradiated with rays in the wavelength range of EUV light is preferably 5% or less, more preferably 3% or less, and particularly preferably 1% or less.
  • the absorption layer 14 is made of a material with a high absorption coefficient for EUV light.
  • a material containing tantalum (Ta) as a main component is preferable as a material having a high absorption coefficient of EUV light.
  • a material containing tantalum (Ta) as a main component means a material containing 20 atomic % or more of Ta.
  • Materials containing Ta as a main component used for the absorption layer 14 include, in addition to Ta, hafnium (Hf), Si, zirconium (Zr), germanium (Ge), boron (B), palladium (Pd), tin (Sn), and chromium.
  • materials containing the above elements other than Ta include TaN, TaNH, TaHf, TaHfN, TaBSi, TaBSiN, TaB, TaBN, TaSi, TaSiN, TaGe, TaGeN, TaZr, TaZrN, TaPd, TaSn, and TaPdN. , TaSn, TaCr, TaMn, TaFe, TaCo, TaAg, TaCd, TaIn, TaSb, TaW and the like.
  • the film thickness of the absorption layer 14 is preferably 20-90 nm.
  • a low reflection layer for inspection light used for inspection of the mask pattern may be formed on the absorption layer 14 .
  • the low-reflection layer is composed of a film that has low reflection in the inspection light used for mask pattern inspection.
  • a reflective mask After forming a pattern in the absorbing layer, it is inspected whether the pattern is formed as designed.
  • an inspection machine that uses light of about 257 nm as inspection light is used. That is, the difference in reflectance of light of about 257 nm, specifically, the difference in reflectance between the surface exposed by removing the absorption layer by pattern formation and the surface of the absorption layer left without being removed by pattern formation. inspected by Here, the former is the protective layer surface. Therefore, if the difference in reflectance with respect to the wavelength of the inspection light between the surface of the protective layer and the surface of the absorption layer is small, the contrast at the time of inspection deteriorates, making accurate inspection impossible. When the difference in reflectance between the protective layer surface and the absorption layer surface with respect to the wavelength of the inspection light is small, the formation of the low-reflection layer improves the contrast during inspection.
  • the low-reflection layer When the low-reflection layer is formed on the absorption layer, the low-reflection layer has a maximum reflectance of 15% or less for the wavelength of the inspection light when the low-reflection layer surface is irradiated with light rays in the wavelength region of the inspection light. is preferred, 10% or less is more preferred, and 5% or less is even more preferred.
  • the low-reflection layer is preferably made of a material having a lower refractive index for the wavelength of the inspection light than that of the absorption layer.
  • a low-reflection layer that satisfies this property contains at least one selected from the group consisting of Ta, Pd, Cr, Si, and Hf and at least one selected from the group consisting of oxygen (O) and N. be.
  • Preferred examples of such a low-reflection layer include a TaPdO layer, TaPdON layer, TaON layer, CrO layer, CrON layer, SiON layer, SiN layer, HfO layer, and HfON layer.
  • the reflective mask blank 10 of the present embodiment includes functional films known in the field of reflective mask blanks, in addition to the reflective multilayer film, the protective layer 13, the absorbing layer 14, and the low-reflection layer formed as necessary. may have.
  • a functional film for example, as described in Japanese Patent Publication No. 2003-501823, it is applied to the back side of the substrate in order to promote electrostatic chucking of the substrate. High dielectric coatings are included.
  • the reflective mask of the present embodiment is obtained by patterning at least the absorption layer (the absorption layer and the low-reflection layer when the low-reflection layer is formed on the absorption layer) of the reflective mask blank of the present embodiment. be done.
  • Example 1 to 4 are examples, and Example 4 is a comparative example.
  • Example 1 a substrate 1 with a reflective layer shown in FIG. 1 was produced.
  • a substrate 11 for film formation a SiO 2 —TiO 2 -based glass substrate (external size: 6 inches (152 mm) square, thickness: 6.3 mm) was used.
  • the thermal expansion coefficient of this glass substrate at 20° C. was 0.02 ⁇ 10 ⁇ 7 /° C.
  • Young's modulus was 67 GPa
  • Poisson's ratio was 0.17
  • specific rigidity was 3.07 ⁇ 10 7 m 2 /s 2 .
  • This glass substrate was polished to form a smooth surface with a surface roughness (rms) of 0.15 nm or less and a flatness of 100 nm or less.
  • a high dielectric coating with a sheet resistance of 100 ⁇ / ⁇ was applied to the rear surface of the substrate 11 by depositing a Cr film with a thickness of 100 nm using a magnetron sputtering method.
  • a substrate 11 (outer shape: 6 inches (152 mm) square, thickness: 6.3 mm) was fixed to a flat plate-shaped ordinary electrostatic chuck via a formed Cr film, and ion beam sputtering was performed on the surface of the substrate 11.
  • a Mo/Si reflective multilayer film with a total film thickness of 272 nm ((2.3 nm + 4.5 nm) x 40) was formed as the reflective layer 12 by repeating 40 cycles of alternately forming a Mo film and a Si film using the method. formed.
  • a Ru layer with a film thickness of 2.5 nm was formed as a protective layer 13 on the Mo/Si reflective multilayer film using an ion beam sputtering method.
  • an anti-adhesion shield made of Al is arranged to cover the target. A portion of the grid where the grid-like openings are provided is circular.
  • an anti-adhesion shield an anti-adhesion shield whose outermost surface was thermally sprayed with Al was used.
  • Ar gas was used as the process gas.
  • the following table shows the product (F ⁇ S) of the radius r of the portion where the grid-like openings are provided, the effective area S of the grid, and the effective area S of the grid and the flow rate F of Ar of the process gas during film formation. Street.
  • the beam voltage was 600 V and the pressure inside the chamber was 2.7 ⁇ 10 ⁇ 2 Pa.
  • the metal X with the highest content in the low refractive index layer is Mo.
  • the metal Y other than the metal constituting the substrate 11, the metal constituting the low refractive index layer, the metal constituting the high refractive index layer, and the metal constituting the protective layer 13 is Al. Therefore, the obtained substrate with a reflective layer was measured by XRF, and the intensity ratio of the peak attributed to Al to the peak attributed to Mo (intensity of the peak attributed to Al/intensity of the peak attributed to Mo ). Peak intensities were calculated using background-subtracted net intensities.
  • the XRF measurement conditions are as follows.
  • X-ray source target tube Rh Excitation voltage/X-ray power: 3 kW
  • Type of analyzing crystal Al PETH (pentaerythritol) Mo:LiF(200) Degree of vacuum: 7 Pa The results are shown in the table below.
  • the surface of the Ru layer was irradiated with EUV light at an incident angle of 6 degrees.
  • the reflected light in the EUV wavelength range at this time is measured using an EUV reflectometer, the minimum value of the in-plane distribution of the peak reflectance in the same wavelength range is obtained, and the surface of the peak reflectance in the same wavelength range in Example 1
  • the increase/decrease rate of the peak reflectance was calculated based on the minimum value of the inner distribution. When the increase/decrease rate of the peak reflectance is a positive value, it represents the increase rate of the peak reflectance, and when it is a negative value, it represents the decrease rate of the peak reflectance.
  • the rate of change in the peak reflectance of EUV light was evaluated according to the following criteria.
  • Increase/decrease rate (%) of the peak reflectance of light in the EUV wavelength region is greater than 0.20%.
  • Increase/decrease rate (%) of peak reflectance of light in the EUV wavelength region is less than 0% (decrease rate (%) is more than 0%)
  • the substrate with the reflective layer is measured by XRF, and the intensity ratio of the peak attributed to Al to the peak attributed to Mo (intensity of the peak attributed to Al/intensity of the peak attributed to Mo) is obtained.
  • the surface of the Ru layer was irradiated with EUV light at an incident angle of 6 degrees.
  • the reflected light in the EUV wavelength range at this time is measured using an EUV reflectometer, the minimum value of the in-plane distribution of the peak reflectance in the same wavelength range is obtained, and the surface of the peak reflectance in the same wavelength range in Example 1
  • the increase/decrease rate of the peak reflectance was calculated based on the minimum value of the inner distribution.
  • Example 5 A substrate with a reflective layer was produced in the same manner as in Example 1, except that an anti-adhesion shield whose outermost surface was thermally sprayed with Y 2 O 3 (yttrium oxide) was used.
  • Y 2 O 3 yttrium oxide
  • the substrate with the reflective layer is measured by XRF, and the intensity ratio of the peak attributed to Al to the peak attributed to Mo (intensity of the peak attributed to Al/intensity of the peak attributed to Mo) is obtained.
  • rice field Further, under the following conditions, the substrate with a reflective layer was measured by XRF, and the intensity ratio of the peak attributed to Y (yttrium) to the peak attributed to Mo (intensity of the peak attributed to Y (yttrium)/Mo attributed peak intensity) was determined. The peak intensity was calculated using the net intensity from which the background was subtracted.
  • X-ray source target tube Rh Excitation voltage/X-ray power: 3 kW
  • Type of analyzing crystal Y PET (pentaerythritol) Mo:LiF(200) Degree of vacuum: 7 Pa
  • the surface of the Ru layer was irradiated with EUV light at an incident angle of 6 degrees.
  • the reflected light in the EUV wavelength range at this time is measured using an EUV reflectometer, the minimum value of the in-plane distribution of the peak reflectance in the same wavelength range is obtained, and the surface of the peak reflectance in the same wavelength range in Example 1
  • the increase/decrease rate of the peak reflectance was calculated based on the minimum value of the inner distribution.
  • the intensity of the peak attributed to Al/the intensity of the peak attributed to Mo was 0.0060 or less, and the evaluation of the increase/decrease rate of the peak reflectance was 0 or more. Therefore, there was no decrease in peak reflectance.
  • Example 5 in which the product (F ⁇ S) of the effective area S of the grid and the flow rate F of Ar of the process gas during film formation is 3600 (cm 2 ⁇ sccm) or less, is the substrate with a reflective layer formed ( The intensity of the peak attributed to Y/the intensity of the peak attributed to Mo) was 0.0060 or less, and the evaluation of the increase/decrease rate of the peak reflectance was ⁇ . Therefore, there was no decrease in peak reflectance. Examples 2 and 3, in which the product (F ⁇ S) of the effective area S of the grid and the flow rate F of Ar in the process gas during film formation is 2500 (cm 2 ⁇ sccm) or less, have a reflective multilayer film formed.
  • Example 4 Intensity of peak attributed to Al/Intensity of peak attributed to Mo was 0.0050 or less.
  • the formed substrate with a reflective layer is ( The intensity of the peak attributed to Al/the intensity of the peak attributed to Mo) exceeded 0.0060, the peak reflectance of EUV light decreased, and the rate of increase/decrease was evaluated as x.
  • Substrate with reflective layer 10 Reflective mask blank 11: Substrate 12: Reflective layer 13: Protective layer 14: Absorbing layer

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JP2012208505A (ja) * 2008-02-27 2012-10-25 Hoya Corp フォトマスクブランク、フォトマスク、反射型マスクブランクおよび反射型マスク並びにこれらの製造方法
JP2013199420A (ja) * 2012-02-21 2013-10-03 Asahi Glass Co Ltd チタニア含有シリカガラス体の製造方法
JP2017082289A (ja) * 2015-10-28 2017-05-18 住友金属鉱山株式会社 成膜方法及びその装置並びに成膜体製造装置
WO2021044890A1 (ja) * 2019-09-04 2021-03-11 Hoya株式会社 多層反射膜付き基板、反射型マスクブランク及び反射型マスク、並びに半導体装置の製造方法

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JPS6345370A (ja) * 1986-08-12 1988-02-26 Nissin Electric Co Ltd イオンビ−ムスパツタリング装置
JP2012208505A (ja) * 2008-02-27 2012-10-25 Hoya Corp フォトマスクブランク、フォトマスク、反射型マスクブランクおよび反射型マスク並びにこれらの製造方法
JP2013199420A (ja) * 2012-02-21 2013-10-03 Asahi Glass Co Ltd チタニア含有シリカガラス体の製造方法
JP2017082289A (ja) * 2015-10-28 2017-05-18 住友金属鉱山株式会社 成膜方法及びその装置並びに成膜体製造装置
WO2021044890A1 (ja) * 2019-09-04 2021-03-11 Hoya株式会社 多層反射膜付き基板、反射型マスクブランク及び反射型マスク、並びに半導体装置の製造方法

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