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WO2011071086A1 - Élément optique pour lithographie par ultraviolet extrême (euv) - Google Patents

Élément optique pour lithographie par ultraviolet extrême (euv) Download PDF

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Publication number
WO2011071086A1
WO2011071086A1 PCT/JP2010/072047 JP2010072047W WO2011071086A1 WO 2011071086 A1 WO2011071086 A1 WO 2011071086A1 JP 2010072047 W JP2010072047 W JP 2010072047W WO 2011071086 A1 WO2011071086 A1 WO 2011071086A1
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WO
WIPO (PCT)
Prior art keywords
layer
reflective
euv
substrate
film
Prior art date
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Ceased
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PCT/JP2010/072047
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English (en)
Japanese (ja)
Inventor
正樹 三上
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AGC Inc
Original Assignee
Asahi Glass Co Ltd
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Filing date
Publication date
Application filed by Asahi Glass Co Ltd filed Critical Asahi Glass Co Ltd
Priority to EP10836006.6A priority Critical patent/EP2511943A4/fr
Priority to KR1020127008116A priority patent/KR20130007533A/ko
Priority to JP2011545229A priority patent/JP5590044B2/ja
Publication of WO2011071086A1 publication Critical patent/WO2011071086A1/fr
Priority to US13/472,002 priority patent/US8986910B2/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
    • H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
    • H01L21/0274—Photolithographic processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/08—Mirrors
    • G02B5/0891—Ultraviolet [UV] mirrors
    • 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
    • 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
    • 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
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/70—Microphotolithographic exposure; Apparatus therefor
    • G03F7/70216—Mask projection systems
    • G03F7/70316—Details of optical elements, e.g. of Bragg reflectors, extreme ultraviolet [EUV] multilayer or bilayer mirrors or diffractive optical elements
    • 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
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/70—Microphotolithographic exposure; Apparatus therefor
    • G03F7/708—Construction of apparatus, e.g. environment aspects, hygiene aspects or materials
    • G03F7/7095—Materials, e.g. materials for housing, stage or other support having particular properties, e.g. weight, strength, conductivity, thermal expansion coefficient
    • G03F7/70958—Optical materials or coatings, e.g. with particular transmittance, reflectance or anti-reflection properties
    • 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
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/70—Microphotolithographic exposure; Apparatus therefor
    • G03F7/708—Construction of apparatus, e.g. environment aspects, hygiene aspects or materials
    • G03F7/70983—Optical system protection, e.g. pellicles or removable covers for protection of mask
    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21K—TECHNIQUES FOR HANDLING PARTICLES OR IONISING RADIATION NOT OTHERWISE PROVIDED FOR; IRRADIATION DEVICES; GAMMA RAY OR X-RAY MICROSCOPES
    • G21K1/00—Arrangements for handling particles or ionising radiation, e.g. focusing or moderating
    • G21K1/06—Arrangements for handling particles or ionising radiation, e.g. focusing or moderating using diffraction, refraction or reflection, e.g. monochromators
    • G21K1/062—Devices having a multilayer structure

Definitions

  • the present invention relates to an optical member for EUV (Extreme Ultraviolet: hereinafter, abbreviated as EUV) used in semiconductor manufacturing or the like, specifically, a substrate with a reflective layer for EUV lithography (hereinafter referred to as “ EUV Lithographic Reflective Layer Substrate “or simply” Reflective Layer Substrate “), EUV Lithographic Reflective Mask Blanks (hereinafter also referred to as” EUV Mask Blank "), and EUV Mask Blank Patterned reflective mask for EUV lithography (hereinafter referred to as “EUV mask” in the present specification), reflective mirror for EUV lithography (hereinafter referred to as “EUV mirror” in the present specification) (hereinafter collectively referred to as “EUV mirror”) Also referred to as an optical member for EUV lithography.
  • EUV mask reflective mask for EUV lithography
  • EUV mirror reflective mirror for EUV lithography
  • EUV mirror also referred to as an optical member for EUV lithography.
  • a photolithography method using visible light or ultraviolet light has been used as a technique for transferring a fine pattern necessary for forming an integrated circuit having a fine pattern on a silicon substrate or the like.
  • the limits of conventional photolithography methods have been approached.
  • the resolution limit of the pattern is about 1 ⁇ 2 of the exposure wavelength, and it is said that the immersion wavelength is about 1 ⁇ 4 of the exposure wavelength, and the immersion of ArF laser (193 nm) is used. Even if the method is used, the limit of about 45 nm is expected.
  • EUV lithography which is an exposure technique using EUV light having a shorter wavelength than an ArF laser, is promising as a next-generation exposure technique using an exposure wavelength shorter than 45 nm.
  • EUV light refers to light having a wavelength in the soft X-ray region or vacuum ultraviolet region, and specifically refers to light having a wavelength of about 10 to 20 nm, particularly about 13.5 nm ⁇ 0.3 nm.
  • a conventional refractive optical system such as photolithography using visible light or ultraviolet light may be used. Can not. For this reason, in the EUV light lithography, a reflective optical system, that is, a reflective photomask and a mirror are used.
  • the mask blank is a laminated body before patterning used for photomask manufacturing.
  • a reflective layer that reflects EUV light and an absorber layer that absorbs EUV light are formed in this order on a glass substrate or the like.
  • a molybdenum (Mo) layer which is a low refractive layer
  • a silicon (Si) layer which is a high refractive layer
  • Mo / Si multilayer reflective film is usually used.
  • the absorber layer a material having a high absorption coefficient for EUV light, specifically, a material mainly composed of chromium (Cr) or tantalum (Ta) is used.
  • Patent Document 1 proposes the use of ruthenium (Ru) as a material for the protective layer.
  • Patent Document 2 proposes a protective layer made of a ruthenium compound (Ru content of 10 to 95 at%) containing Ru and at least one selected from Mo, Nb, Zr, Y, B, Ti and La. Has been.
  • Patent Document 3 proposes a multilayer protective layer of Ru / Si pairs.
  • a mirror used in EUV lithography has a structure in which a reflective layer that reflects EUV light is formed on a substrate such as a glass substrate.
  • a reflective layer since a high EUV light reflectance can be achieved, a multilayer reflective film in which a high refractive layer and a low refractive index layer are alternately laminated a plurality of times is usually used. Therefore, as a mirror used in EUV light lithography, a multilayer mirror in which a multilayer reflective film is formed on such a substrate is usually used (see Patent Document 4).
  • a protective layer protection capping layer
  • Patent Document 4 describes that a specific capping layer (protective layer) is provided on a reflective layer because the EUV mirror can withstand chemical and physical attack.
  • the multilayer mirror described in Patent Document 4 includes a protective capping layer made of a material selected from ruthenium (Ru) and rhodium (Rh), and compounds and alloys thereof.
  • the steps performed when manufacturing the mask blank and mirror, and the steps performed when manufacturing a photomask from the mask blank for example, cleaning, defect inspection, heating step, In each step of dry etching and defect correction
  • the Ru protective layer, and further the uppermost layer of the multilayer reflective film in the case of Mo / Si multilayer reflective film, Si layer
  • the EUV light reflectance is reduced when EUV light is irradiated on the surface of the protective layer.
  • the decrease in the EUV light reflectivity during EUV exposure is a problem because it progresses over time, so that it is necessary to change the exposure conditions in the middle, and the life of the photomask and mirror is shortened.
  • a process performed when manufacturing a mask blank or a mirror or a process performed when manufacturing a photomask from the mask blank for example, cleaning, defect inspection, heating process, dry etching, defect correction
  • the Ru protective layer and further the uppermost layer of the multilayer reflective film are oxidized, and the EUV light reflectance when the protective layer surface is irradiated with EUV light is reduced. May be simply referred to as “reduction in EUV light reflectance due to oxidation of the Ru protective layer”.
  • the protective layer described in Patent Document 2 is described as being capable of sufficiently obtaining the anti-oxidation effect of the multilayer reflective film without causing a decrease in the reflectance of the multilayer reflective film.
  • the decrease in the reflectance is caused by the Si layer and the Ru protective layer, which are the uppermost layers of the multilayer reflective film, during the Ru protective layer film formation or the subsequent heat treatment or the like.
  • Si layer and the Ru protective layer which are the uppermost layers of the multilayer reflective film, during the Ru protective layer film formation or the subsequent heat treatment or the like.
  • the EUV light reflectivity is reduced by oxidation of the Ru protective layer as described above.
  • the protective layer described in Patent Document 3 is a Ru / Si pair multilayer protective layer, which causes a problem of a decrease in reflectance due to oxidation of the Si layer, and the Ru layer has an EUV light absorption coefficient higher than that of the Si layer. It is intended to solve both of the problems that the film thickness cannot be increased due to its high thickness, but is it intended to reduce the EUV light reflectance due to oxidation of the Ru protective layer as described above? Is unknown.
  • the present invention provides an optical member such as an EUV mask blank or an EUV mirror in which a decrease in EUV light reflectance due to oxidation of the Ru protective layer is suppressed, and a functional film used for manufacturing the optical member.
  • An object is to provide an attached substrate.
  • the present inventors can suppress a decrease in EUV light reflectance due to oxidation of the Ru protective layer by inserting a thin Mo layer between the Ru protective layers. I found. The inventors have found that it is effective to set the film thickness of the Mo intermediate layer in the protective layer within a specific range.
  • the present invention has been made based on the above-mentioned findings of the present inventors, and an EUV in which a reflective layer that reflects EUV light and a protective layer that protects the reflective layer are formed on a substrate in this order.
  • a substrate with a reflective layer for lithography The reflective layer is a Mo / Si multilayer reflective film;
  • the protective layer is laminated from the reflective layer side in the order of a first layer made of a Ru layer or a Ru compound layer, a second layer made of a Mo layer, and a third layer made of a Ru layer or a Ru compound layer.
  • a substrate with a reflective layer for EUV lithography (hereinafter also referred to as “substrate with a reflective layer of the present invention”) having a three-layer structure is provided. It is preferable that the uppermost layer of the reflective layer made of the Mo / Si multilayer reflective film is a Si film, and the protective layer is formed in contact with the Si film surface.
  • the film thickness of the second layer is 0.2 nm or more and 2 nm or less, or 1/2 or less of the total film thickness of the protective layer, whichever is smaller. It is preferable to satisfy
  • the total thickness of the protective layer is preferably 1 to 10 nm.
  • the surface roughness rms of the protective layer surface is 0.5 nm0.5 or less.
  • the present invention is a reflective mask blank for EUV lithography in which an absorber layer is formed on the protective layer of the above-described substrate with a reflective layer of the present invention (hereinafter also referred to as “EUV mask blank of the present invention”). I will provide a.
  • the absorber layer is preferably formed of a material mainly composed of tantalum (Ta).
  • the etching selectivity between the protective layer and the absorber layer when dry etching is performed using a chlorine-based gas as an etching gas is preferably 10 or more.
  • a low reflection layer for inspection light used for inspection of a mask pattern which is formed of a material mainly containing tantalum (Ta), is provided on the absorber layer. preferable.
  • the reflected light on the surface of the protective layer with respect to the wavelength of light used for inspection of the pattern formed on the absorber layer, and the surface on the surface of the low reflection layer is preferably 30% or more.
  • the present invention also provides a reflective mask for EUV lithography (hereinafter also referred to as “the EUV mask of the present invention”) obtained by patterning the EUV mask blank of the present invention described above.
  • EUV mirror of the present invention using the substrate with a reflective layer for EUV lithography is provided.
  • the present invention also provides a method for manufacturing a semiconductor integrated circuit, wherein a semiconductor integrated circuit is manufactured by exposing an object to be exposed using the EUV mask of the present invention described above.
  • the EUV mask produced using the EUV mask blank of the present invention is a highly reliable EUV mask in which the change in EUV light reflectance with time is small during EUV exposure, and is an integrated pattern consisting of fine patterns. Useful for the manufacture of circuits.
  • FIG. 1 is a schematic cross-sectional view showing an embodiment of an EUV mask blank of the present invention.
  • FIG. 2 is a schematic cross-sectional view showing an embodiment in which a low reflection layer is formed on the absorber layer of the EUV mask blank of FIG.
  • FIG. 3 is a schematic cross-sectional view showing a state in which the absorber layer 14 and the low reflective layer 15 of the EUV mask blank 1 ′ of FIG.
  • FIG. 4 is a schematic cross-sectional view showing an embodiment of the EUV mirror of the present invention.
  • FIG. 1 is a schematic cross-sectional view showing an embodiment of the EUV mask blank of the present invention.
  • a reflective layer 12 that reflects EUV light and a protective layer 13 for protecting the reflective layer 12 are formed on a substrate 11 in this order.
  • the protective layer 13 includes, from the reflective layer 12 side, the first layer 13a made of the Ru layer or the Ru compound layer, the second layer 13b made of the Mo layer, and the Ru layer or the Ru compound. It has a three-layer structure in which the third layer 13c composed of layers is laminated in this order.
  • An absorber layer 14 is formed on the protective layer 13 having a three-layer structure.
  • FIG. 4 is a schematic sectional view showing an embodiment of the EUV mirror of the present invention.
  • a reflective layer 12 that reflects EUV light and a protective layer 13 that protects the reflective layer 12 are formed on a substrate 11 in this order.
  • the protective layer 13 includes, from the reflective layer 12 side, the first layer 13a made of the Ru layer or the Ru compound layer, the second layer 13b made of the Mo layer, and the Ru layer or Ru. It has a three-layer structure in which the third layer 13c made of a compound layer is laminated in this order.
  • a member having a multilayer film that reflects EUV light such as a mask blank or a mirror, is also referred to as an “EUV optical member”.
  • the substrate 11 is required to satisfy the characteristics as a substrate for an EUV mask blank. Therefore, it is important that the substrate 11 has a low thermal expansion coefficient.
  • the thermal expansion coefficient of the substrate 11 is preferably 0 ⁇ 1.0 ⁇ 10 ⁇ 7 / ° C., more preferably 0 ⁇ 0.3 ⁇ 10 ⁇ 7 / ° C., further preferably 0 ⁇ It is 0.2 ⁇ 10 ⁇ 7 / ° C., more preferably 0 ⁇ 0.1 ⁇ 10 ⁇ 7 / ° C., particularly preferably 0 ⁇ 0.05 ⁇ 10 ⁇ 7 / ° C.
  • the substrate preferably has excellent smoothness, flatness, and resistance to a cleaning liquid used for cleaning a mask blank or a photomask after pattern formation.
  • the substrate 11 is made of glass having a low thermal expansion coefficient, such as SiO 2 —TiO 2 glass, but is not limited to this. Crystallized glass, quartz glass, silicon, A substrate made of metal or the like can also be used. A film such as a stress correction film may be formed on the substrate 11. Since the substrate 11 has a smooth surface with a surface roughness rms of 0.15 nm or less and a flatness of 100 nm or less, high reflectivity and transfer accuracy can be obtained in a photomask after pattern formation. preferable. The size, thickness, etc.
  • the substrate 11 are appropriately determined by the design value of the mask.
  • SiO 2 —TiO 2 glass having an outer diameter of 6 inches (152.4 mm) square and a thickness of 0.25 inches (6.3 mm) was used.
  • the size of the substrate used for the mirror is appropriately determined depending on the design value of the exposure machine, and a substrate having a diameter of about 50 to 500 mm is usually used.
  • the mask blank substrate has a rectangular shape such as a square in plan view.
  • the mirror substrate has many circular, elliptical and polygonal planar shapes. It is preferable that the surface of the substrate 11 on the side where the reflective layer 12 is formed has no defects.
  • the depth of the concave defect and the height of the convex defect are not more than 2 nm so that the phase defect does not occur due to the concave defect and / or the convex defect. It is preferable that the half width of the defect and the convex defect is 60 nm or less.
  • the characteristic of the reflective layer 12 of the EUV optical member is a high EUV light reflectance. Specifically, when the surface of the reflective layer 12 is irradiated with light in the wavelength region of EUV light at an incident angle of 6 degrees, the maximum value of light reflectance near a wavelength of 13.5 nm is preferably 60% or more, More preferably, it is 65% or more. Even when the protective layer 13 is provided on the reflective layer 12, the maximum value of the light reflectance near the wavelength of 13.5 nm is preferably 60% or more, and more preferably 65% or more. preferable.
  • the reflective layer since a high reflectance can be achieved in the EUV wavelength region, a multilayer reflective film in which a high refractive index film and a low refractive index film are alternately laminated a plurality of times is used.
  • the EUV optical member of the present invention uses a Mo / Si multilayer reflective film in which a Mo film as a low refractive index film and a Si film as a high refractive index film are alternately laminated a plurality of times.
  • the uppermost layer of the laminated Mo / Si multilayer reflective film is preferably a Si film.
  • a Mo / Si multilayer reflective film in order to obtain the reflective layer 12 having a maximum EUV light reflectance of 60% or more, a Mo layer having a film thickness of 2.3 ⁇ 0.1 nm, a film thickness of 4.5 ⁇ A 0.1 nm Si layer may be stacked so that the number of repeating units is 30 to 60.
  • each layer which comprises Mo / Si multilayer reflective film so that it may become desired thickness using film-forming methods, such as a magnetron sputtering method and an ion beam sputtering method.
  • film-forming methods such as a magnetron sputtering method and an ion beam sputtering method.
  • a Mo target is used as a target and Ar gas (gas pressure 1.3 ⁇ 10 ⁇ 2 Pa to 2.7 ⁇ 10 ⁇ as a sputtering gas). 2 Pa)
  • an Mo layer is formed to have a thickness of 2.3 nm at an ion acceleration voltage of 300 to 1500 V and a film formation rate of 0.03 to 0.30 nm / sec.
  • the Si layer is formed so that the thickness is 4.5 nm at 30 nm / sec. With this as one period, the Mo / Si multilayer reflective film is formed by laminating the Mo layer and the Si layer for 40 to 50 periods.
  • the protective layer 13 is provided for the purpose of protecting the reflective layer 12 so that the reflective layer 12 is not damaged by the etching process when the absorber layer 14 is patterned by an etching process, usually a dry etching process. Therefore, as the material of the protective layer 13, a material that is not easily affected by the etching process of the absorber layer 14, that is, the etching rate is slower than that of the absorber layer 14 and is not easily damaged by the etching process is selected. Moreover, it is preferable that the protective layer 13 itself also has a high EUV light reflectivity so that the EUV light reflectivity at the reflective layer 12 is not impaired even after the protective layer 13 is formed.
  • Ru is used as a constituent material of the protective layer of the EUV optical member.
  • the first layer 13a and the third layer 13c of the protective layer 13 having a three-layer structure are Ru layers or Ru compound layers.
  • both the first layer 13a and the third layer 13c may be Ru layers or Ru compound layers.
  • one of the first layer 13a and the third layer 13c may be a Ru layer and the other may be a Ru compound layer.
  • the Ru compound is preferably at least one selected from the group consisting of RuB, RuNb and RuZr.
  • the content rate of Ru is 50 at% or more, 80 at% or more, especially 90 at% or more.
  • the Nb content is preferably about 10 to 40 at%.
  • the first layer 13a and the third layer 13c preferably have a Si content of 5 at% or less, more preferably 3 at% or less, and even more preferably 1 at% or less.
  • the second layer 13b of the three-layer protective layer 13 is a Mo layer, thereby suppressing a decrease in EUV light reflectance due to oxidation of the Ru protective layer.
  • the reason why the EUV light reflectance lowering due to oxidation of the Ru protective layer is suppressed by using the Mo layer as the second layer 13b of the protective layer 13 having a three-layer structure is considered as follows.
  • a process performed when manufacturing a photomask from the mask blank for example, cleaning, defect inspection, heating process, dry etching, defect correction process
  • the protective layer 13 having a three-layer structure is oxidized from the third layer 13c, which is the uppermost layer, followed by the second layer 13b and the second layer 13b. Oxidation proceeds in the order of the first layer 13a.
  • each Ru layer can be reduced to about 1/2, A Ru layer having low crystallinity and few crystal grain boundaries can be obtained. Thereby, the diffusion of oxygen through the grain boundaries in the Ru layer can be effectively suppressed.
  • the Mo / Si multilayer reflective film below the first layer 13a is oxidized, more specifically, the uppermost Si film of the Mo / Si multilayer reflective film is oxidized. As a result, it is considered that the decrease in EUV light reflectance due to oxidation of the Ru protective layer is suppressed.
  • Mo constituting the second layer 13b is a material having a high EUV light reflectivity so as to be used also for the Mo / Si multilayer reflective film, and the film thickness of the second layer 13b is small as will be described later. Therefore, the decrease in EUV light reflectance due to oxidation of the second layer (Mo layer) (reduction in EUV light reflectance when the surface of the protective layer 13 is irradiated with EUV light) is slight and can be ignored.
  • a Ru protective layer is formed on the Mo / Si multilayer reflective film, Si in the Si film that is the uppermost layer of the Mo / Si multilayer reflective film may diffuse into the Ru protective layer, which may be a problem.
  • the EUV optical member of the present invention even when a situation occurs in which Si in the Si film diffuses into the Ru layer that is the first layer 13a or the Ru compound layer, the Mo that is the second layer 13b. Due to the presence of the layer, Si is suppressed from diffusing into the third layer 13c above the second layer 13b. Therefore, even when a situation occurs in which Si in the Si film diffuses into the Ru protective layer when the Ru protective layer is formed, Si diffuses into the Ru protective layer, more specifically, the uppermost layer of the Ru protective layer. Si diffusion into the third layer 13c can be suppressed to a minimum.
  • the content of Si in the Mo layer forming the second layer 13b is preferably 5 at% or less, more preferably 3 at% or less, and even more preferably 1 at% or less.
  • the Mo layer forming the second layer 13b preferably has a Mo content of 60 at% or more, particularly 80 at% or more, and more preferably 90 at% or more.
  • the thickness of the second layer 13b is preferably 0.2 nm or more. If the film thickness is less than 0.2 nm, the formation of the second layer 13b may be incomplete depending on the film formation conditions, and the effect of suppressing the decrease in EUV light reflectance due to oxidation of the Ru protective layer may be insufficient. . On the other hand, the film thickness of the second layer 13b preferably satisfies the smaller one of 2 nm or less or 1/2 or less of the total film thickness of the protective layer 13 in consideration of the influence on the EUV characteristics.
  • the Ru layer or the Ru compound exhibits a function as a protective layer of the EUV optical member, that is, a function of protecting the reflective layer 12 so as not to be damaged by the etching process.
  • the first layer 13a and the third layer 13c are layers. If the film thickness of the second layer 13b is larger than 1 ⁇ 2 of the total film thickness of the protective layer 13, the film thickness of the first layer 13a and the third layer 13c becomes small. There is a risk that the function of will not be able to be demonstrated.
  • the film thickness of the second layer 13b is more preferably 0.3 nm to 1 nm, and further preferably 0.3 nm to 0.6 nm.
  • the total film thickness of the protective layer 13 having a three-layer structure is preferably 1 to 10 nm because the EUV light reflectance can be increased and etching resistance can be obtained.
  • the total thickness of the protective layer 13 is more preferably 1 to 5 nm, and further preferably 2 to 4 nm.
  • the thicknesses of the first layer 13a and the third layer 13c are not particularly limited, and the preferred range of the total thickness of the protective layer 13 described above and the second layer 13b It can select suitably in the range with which the suitable range of a film thickness is satisfy
  • the films of the first layer 13a and the third layer 13c The thickness is preferably 0.6 to 3 nm, and more preferably 0.8 to 1.8 nm. Moreover, it is preferable that the difference of the film thickness of the 1st layer 13a and the 3rd layer 13c is 0.5 nm or less.
  • the surface roughness of the protective layer 13 surface is preferably 0.5 nm or less.
  • the surface roughness rms of 0.5 nm or less means that the root mean square surface roughness is 0.5 nm or less. If the surface roughness of the surface of the protective layer 13 is large, the surface roughness of the absorber layer 14 formed on the protective layer 13 increases, and the edge roughness of the pattern formed on the absorber layer 14 increases. The dimensional accuracy of the pattern deteriorates. Since the influence of edge roughness becomes more prominent as the pattern becomes finer, the surface of the absorber layer 14 is required to be smooth.
  • the surface roughness rms of the surface of the protective layer 13 is 0.5 nm or less, the surface of the absorber layer 14 formed on the protective layer 13 is sufficiently smooth, and the dimensional accuracy of the pattern deteriorates due to the influence of edge roughness. There is no fear.
  • the surface roughness rms of the surface of the protective layer 13 is more preferably 0.4 nm or less, and further preferably 0.3 nm or less.
  • Each layer of the protective layer 13 having a three-layer structure can be formed using a film forming method such as a magnetron sputtering method or an ion beam sputtering method.
  • a film forming method such as a magnetron sputtering method or an ion beam sputtering method.
  • the Ru layer is formed as the first layer 13a and the third layer 13c using the ion beam sputtering method
  • the Ru target may be used as a target and discharged in an argon (Ar) atmosphere.
  • ion beam sputtering may be performed under the following conditions.
  • Sputtering gas Ar (gas pressure: 1.0 ⁇ 10 ⁇ 1 to 10 ⁇ 10 ⁇ 1 Pa, preferably 1.0 ⁇ 10 ⁇ 1 to 5.0 ⁇ 10 ⁇ 1 Pa, more preferably 1.0 ⁇ 10 ⁇ 1 to 3.0 ⁇ 10 ⁇ 1 Pa).
  • Input power (for each target): 30 to 1000 W, preferably 50 to 750 W, more preferably 80 to 500 W.
  • Film forming speed 0.1 to 6 nm / sec, preferably 0.1 to 4.5 nm / sec, more preferably 0.1 to 3 nm / sec.
  • the Mo target when forming the Mo layer as the second layer 13b using the ion beam sputtering method, the Mo target may be used as a target and discharged in an argon (Ar) atmosphere.
  • ion beam sputtering may be performed under the following conditions.
  • Sputtering gas Ar (gas pressure: 1.3 ⁇ 10 ⁇ 2 Pa to 2.7 ⁇ 10 ⁇ 2 Pa).
  • -Ion acceleration voltage 300-1500V.
  • Film forming speed 0.005 to 0.3 nm / sec, preferably 0.01 to 0.2 nm / sec, more preferably 0.02 to 0.1 nm / sec.
  • the substrate with a reflective layer of the present invention in which the multilayer reflective film 12 and the protective layer 13 are formed in this order on the film forming surface of the substrate 11 is obtained.
  • the substrate with a reflective layer of the present invention is a precursor of an EUV mask blank, and an absorber layer according to the procedure described later on the protective layer of the substrate with a reflective layer of the present invention, and further, if necessary, The EUV mask blank of the present invention is obtained by forming a low reflection layer on the absorber layer.
  • the substrate with a reflective layer of the present invention can also be used as an EUV mirror.
  • the decrease in EUV light reflectance before and after the heat-treatment is 7% or less, 6% The following is more preferable.
  • it heated on conditions severer than the heating process implemented at the time of the heating process implemented at the time of mask blank and mirror manufacture, and a mask blank at the time of manufacture. Processing was carried out.
  • the characteristic particularly required for the absorber layer 14 is that the EUV light reflectance is extremely low. Specifically, when the surface of the absorber layer 14 is irradiated with light in the wavelength region of EUV light, the maximum light reflectance near a wavelength of 13.5 nm is preferably 0.5% or less, 0.1% The following is more preferable.
  • the material is composed of a material having a high EUV light absorption coefficient, and it is preferable that the material is mainly composed of tantalum (Ta).
  • the absorber layer 14 include those containing Ta, B, Si, and nitrogen (N) in the ratios described below (TaBSiN film).
  • B content 1 at% or more and less than 5 at%, preferably 1 to 4.5 at%, more preferably 1.5 to 4 at%.
  • Si content 1 to 25 at%, preferably 1 to 20 at%, more preferably 2 to 12 at%.
  • the absorber layer 14 having the above composition has an amorphous crystal state and excellent surface smoothness.
  • the absorber layer 14 having the above composition preferably has a surface roughness of 0.5 nm or less. If the surface roughness of the surface of the absorber layer 14 is large, the edge roughness of the pattern formed on the absorber layer 14 increases, and the dimensional accuracy of the pattern deteriorates. Since the influence of edge roughness becomes more prominent as the pattern becomes finer, the surface of the absorber layer 14 is required to be smooth. If the surface roughness of the surface of the absorber layer 14 is 0.5 nm or less, the surface of the absorber layer 14 is sufficiently smooth, so that the dimensional accuracy of the pattern does not deteriorate due to the influence of edge roughness.
  • the surface roughness of the surface of the absorber layer 14 is more preferably 0.4 nm or less, and further preferably 0.3 nm or less.
  • the etching rate when performing dry etching using a chlorine-based gas as an etching gas is high, and the etching selectivity with the protective layer 13 is 10 or more.
  • the etching selectivity can be calculated using the following equation (1).
  • Etching selectivity (etching rate of absorber layer 14) / (etching rate of protective layer 13) (1)
  • the etching selection ratio is preferably 10 or more, more preferably 11 or more, and further preferably 12 or more.
  • the thickness of the absorber layer 14 is preferably 50 to 100 nm.
  • the absorption layer 14 having the above-described configuration can be formed using a film forming method such as a sputtering method such as a magnetron sputtering method or an ion beam sputtering method.
  • a low reflection layer 15 for inspection light used for inspection of a mask pattern is preferably formed on the absorber layer 14 like an EUV mask blank 1 ′ shown in FIG.
  • an inspection machine that normally 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 surface where the absorber layer 14 is removed by pattern formation and the surface of the absorber layer 14 that remains without being removed by pattern formation, It is inspected by the difference in reflectance.
  • the former is the surface of the protective layer 13. Therefore, if the difference in reflectance between the surface of the protective layer 13 and the surface of the absorber layer 14 with respect to the wavelength of the inspection light is small, the contrast at the time of inspection deteriorates and accurate inspection cannot be performed.
  • the absorber layer 14 having the above-described configuration has extremely low EUV light reflectance, and has excellent characteristics as an absorption layer of an EUV mask blank.
  • the light reflectance is not always sufficient. It's not low.
  • the difference between the reflectance of the surface of the absorber layer 14 and the reflectance of the surface of the protective layer 13 at the wavelength of the inspection light becomes small, and there is a possibility that sufficient contrast during inspection cannot be obtained. If sufficient contrast at the time of inspection is not obtained, pattern defects cannot be sufficiently determined in mask inspection, and accurate defect inspection cannot be performed.
  • the low reflection layer 15 is formed on the absorber layer 14 to improve the contrast at the time of inspection.
  • the light reflectance is extremely low.
  • the low reflection layer 15 formed for such a purpose has a maximum light reflectance of 15% or less, preferably 10% or less when irradiated with light in the wavelength region of inspection light. More preferably, it is 5% or less. If the light reflectance at the wavelength of the inspection light in the low reflection layer 15 is 15% or less, the contrast at the time of the inspection is good. Specifically, the contrast between the reflected light having the wavelength of the inspection light on the surface of the protective layer 13 and the reflected light having the wavelength of the inspection light on the surface of the low reflective layer 15 is 30% or more.
  • R 2 at the wavelength of the inspection light is a reflectance at the surface of the protective layer 13
  • R 1 is a reflectance at the surface of the low reflective layer 15.
  • the R 1 and R 2 are measured in a state where patterns are formed on the absorber layer 14 and the low reflection layer 15 of the EUV mask blank 1 ′ shown in FIG. 2 (that is, the state shown in FIG. 3).
  • the R 2 is a value measured on the surface of the protective layer 13 exposed to the outside after the absorber layer 14 and the low reflection layer 15 are removed by pattern formation in FIG. 3, and R 1 is not removed by pattern formation. It is a value measured on the surface of the remaining low reflection layer 15.
  • the contrast represented by the above formula (2) is more preferably 45% or more, further preferably 60% or more, and particularly preferably 80% or more.
  • the low reflection layer 15 is preferably made of a material whose refractive index at the wavelength of the inspection light is lower than that of the absorber layer 14, and its crystal state is preferably amorphous.
  • a low reflection layer 15 include those containing Ta, B, Si and oxygen (O) in the ratios described below (low reflection layer (TaBSiO)).
  • B content 1 at% or more and less than 5 at%, preferably 1 to 4.5 at%, more preferably 1.5 to 4 at%.
  • -Si content 1 to 25 at%, preferably 1 to 20 at%, more preferably 2 to 10 at%.
  • the low reflective layer 15 include those containing Ta, B, Si, O, and N in the ratios described below (low reflective layer (TaBSiON)).
  • B content 1 at% or more and less than 5 at%, preferably 1 to 4.5 at%, more preferably 2 to 4.0 at%.
  • -Si content 1 to 25 at%, preferably 1 to 20 at%, more preferably 2 to 10 at%.
  • the low reflective layer (TaBSiO) or (TaBSiON) has the above-described configuration, its crystal state is amorphous and its surface is excellent in smoothness.
  • the surface roughness rms of the surface of the low reflective layer (TaBSiO) or (TaBSiON) is preferably 0.5 nm or less.
  • the surface of the absorber layer 14 is required to be smooth in order to prevent deterioration in the dimensional accuracy of the pattern due to the influence of edge roughness. Since the low reflection layer 15 is formed on the absorber layer 14, the surface thereof is required to be smooth for the same reason.
  • the surface roughness rms of the surface of the low reflection layer 15 is 0.5 nm or less, the surface of the low reflection layer 15 is sufficiently smooth, and there is no possibility that the dimensional accuracy of the pattern is deteriorated due to the influence of edge roughness.
  • the surface roughness rms of the surface of the low reflective layer 15 is more preferably 0.4 nm or less, and further preferably 0.3 nm or less.
  • the total thickness of the absorber layer 14 and the low reflection layer 15 is preferably 55 to 130 nm. Further, if the thickness of the low reflection layer 15 is larger than the thickness of the absorber layer 14, the EUV light absorption characteristics in the absorber layer 14 may be deteriorated. Therefore, the thickness of the low reflection layer 15 is determined by the absorber layer. It is preferred that the thickness be less than 14. For this reason, the thickness of the low reflective layer 15 is preferably 5 to 30 nm, and more preferably 10 to 20 nm.
  • the low reflection layer (TaBSiO) or (TaBSiON) can be formed using a film forming method such as a magnetron sputtering method or a sputtering method such as an ion beam sputtering method.
  • the reason why the low reflection layer 15 is preferably formed on the absorber layer 14 as in the EUV mask blank 1 'shown in FIG. 2 is that the wavelength of the inspection light for the pattern and the wavelength of the EUV light are different. is there. Therefore, when EUV light (around 13.5 nm) is used as the pattern inspection light, it is considered unnecessary to form the low reflection layer 15 on the absorber layer 14.
  • the wavelength of the inspection light tends to shift to the short wavelength side as the pattern size becomes smaller, and it is conceivable that it will shift to 193 nm and further to 13.5 nm in the future.
  • the wavelength of the inspection light is 13.5 nm, it is considered unnecessary to form the low reflection layer 15 on the absorber layer 14.
  • the EUV mask blank of the present invention may have a functional film known in the field of EUV mask blanks.
  • a functional film for example, in order to promote electrostatic chucking of a substrate as described in JP-A-2003-501823 (incorporated as the disclosure of the present specification), Examples include a high dielectric coating applied to the back side of the substrate.
  • the back surface of the substrate refers to the surface of the substrate 11 in FIG. 1 opposite to the side on which the reflective layer 12 is formed.
  • the electrical conductivity and thickness of the constituent material are selected so that the sheet resistance is 100 ⁇ / ⁇ or less.
  • the constituent material of the high dielectric coating can be widely selected from those described in known literature.
  • a high dielectric constant coating described in JP-A-2003-501823 specifically, a coating made of silicon, TiN, molybdenum, chromium, or TaSi can be applied.
  • the thickness of the high dielectric coating can be, for example, 10 to 1000 nm.
  • the high dielectric coating can be formed using a known film formation method, for example, a sputtering method such as a magnetron sputtering method or an ion beam sputtering method, a CVD method, a vacuum evaporation method, or an electrolytic plating method.
  • a sputtering method such as a magnetron sputtering method or an ion beam sputtering method
  • CVD method a vacuum evaporation method
  • electrolytic plating method an electrolytic plating method.
  • the EUV mirror of the present invention may also have the above-described high dielectric coating.
  • the EUV mask of the present invention is manufactured by patterning at least the absorber layer of the EUV mask blank of the present invention (when the low reflection layer is formed on the absorber layer, the absorber layer and the low reflection layer). It becomes possible.
  • the patterning method of the absorber layer (when the low-reflection layer is formed on the absorber layer, the absorber layer and the low-reflection layer) is not particularly limited.
  • the absorber layer (low reflection on the absorber layer)
  • a resist is applied on the absorber layer and the low reflection layer to form a resist pattern, and this is used as a mask to form the absorber layer (the low reflection layer on the absorber layer).
  • a method of etching the absorber layer and the low reflection layer can be employed.
  • the resist material and resist pattern drawing method can be selected as appropriate in consideration of the material of the absorber layer (in the case where a low reflection layer is formed on the absorber layer, the absorber layer and the low reflection layer). Good.
  • the etching method of the absorber layer is not particularly limited, and dry etching such as reactive ion etching or wet etching is employed. it can. After patterning the absorber layer (when the low reflection layer is formed on the absorber layer, the absorber layer and the low reflection layer), the resist is stripped with a stripping solution to obtain the EUV mask of the present invention. It is done.
  • the present invention can be applied to a method for manufacturing a semiconductor integrated circuit by a photolithography method using EUV light as an exposure light source.
  • a substrate such as a silicon wafer coated with a resist is placed on a stage, and the EUV mask is installed in a reflective exposure apparatus configured by combining a reflecting mirror.
  • the EUV light is irradiated from the light source to the EUV mask through the reflecting mirror, and the EUV light is reflected by the EUV mask and irradiated to the substrate coated with the resist.
  • the circuit pattern is transferred onto the substrate.
  • the substrate on which the circuit pattern has been transferred is subjected to development to etch the photosensitive portion or the non-photosensitive portion, and then the resist is peeled off.
  • a semiconductor integrated circuit is manufactured by repeating such steps.
  • Example 1 a mask blank 1 ′ shown in FIG. 2 was produced.
  • a SiO 2 —TiO 2 glass substrate (outer dimensions 6 inches (152.4 mm) square, thickness 6.3 mm) was used.
  • This glass substrate has a thermal expansion coefficient of 0.2 ⁇ 10 ⁇ 7 / ° C., a Young's modulus of 67 GPa, a Poisson's ratio of 0.17, and a specific rigidity of 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 (not shown) having a sheet resistance of 100 ⁇ / ⁇ was applied to the back surface of the substrate 11 by depositing a Cr film having a thickness of 100 nm using a magnetron sputtering method.
  • a substrate 11 (outer dimensions 6 inches (152.4 mm) square, thickness 6.3 mm) is fixed to a normal electrostatic chuck having a flat plate shape by using the formed Cr film, and ions are formed on the surface of the substrate 11.
  • the Mo / Si multilayer reflective film (reflective layer) having a total film thickness of 340 nm ((2.3 nm + 4.5 nm) ⁇ 50) is obtained by repeating 50 cycles of alternately forming the Mo film and the Si film by using the beam sputtering method. 12) was formed.
  • the uppermost layer of the Mo / Si multilayer reflective film is a Si film.
  • the conditions for forming the Mo film and the Si film are as follows.
  • Mo film formation conditions -Target: Mo target.
  • Sputtering gas Ar gas (gas pressure: 0.02 Pa).
  • Film forming speed 0.064 nm / sec.
  • -Film thickness 2.3 nm.
  • Target Si target (boron doped).
  • Sputtering gas Ar gas (gas pressure: 0.02 Pa).
  • -Voltage 700V.
  • Film forming speed 0.077 nm / sec. -Film thickness: 4.5 nm.
  • a Ru layer was formed as a first layer 13a of the protective layer 13 on the reflective layer 12 by using an ion beam sputtering method.
  • the conditions for forming the first layer 13a are as follows.
  • Target Ru target.
  • Sputtering gas Ar gas (gas pressure: 0.02 Pa).
  • -Voltage 700V.
  • Film forming speed 0.052 nm / sec.
  • -Film thickness 1.25 nm.
  • a Mo layer was formed as the second layer 13b of the protective layer 13 by using an ion beam sputtering method.
  • the conditions for forming the second layer 13b are as follows. -Target: Mo target. Sputtering gas: Ar gas (gas pressure: 0.02 Pa). -Voltage: 700V. Film forming speed: 0.064 nm / sec. -Film thickness: 0.5 nm.
  • a Ru layer was formed as the third layer 13c of the protective layer 13 by ion beam sputtering.
  • the formation conditions of the third layer 13c are as follows.
  • a TaBSiN layer is formed as the absorber layer 14 on the protective layer 13, more specifically, on the third layer 13 c of the protective layer 13 by using a magnetron sputtering method.
  • the conditions for forming the TaBSiN layer are as follows.
  • Target TaBSi compound target (composition ratio: Ta 80 at%, B 10 at%, Si 10 at%).
  • Sputtering gas Mixed gas of Ar and N 2 (Ar: 86% by volume, N 2 : 14% by volume, gas pressure: 0.3 Pa).
  • -Input power 150W.
  • Film forming speed 0.12 nm / sec.
  • -Film thickness 60 nm.
  • TaBSiON layer deposition conditions Target: TaBSi target (composition ratio: Ta 80 at%, B 10 at%, Si 10 at%).
  • Sputtering gas Ar, N 2 and O 2 mixed gas (Ar: 60% by volume, N 2 : 20% by volume, O 2 : 20% by volume, gas pressure: 0.3 Pa).
  • -Input power 150W.
  • Film forming speed 0.18 nm / sec.
  • -Film thickness 10 nm.
  • the surface roughness rms of the protective layer 13 was 0.15 nm.
  • (3) Heat treatment resistance The sample formed up to the protective layer 13 by the above procedure was subjected to heat treatment (atmosphere) at 210 ° C. for 10 minutes. Before and after this treatment, the surface of the protective layer 13 was irradiated with EUV light (wavelength 13.5 nm), and the EUV reflectivity was measured using an EUV reflectometer (MBR (product name) manufactured by AIXUV). The decrease in EUV reflectance before and after this treatment was 5.4%.
  • Reflection characteristics About the sample formed to the protective layer 13 by said procedure, the reflectance of the pattern test
  • the EUV light (wavelength 13.5nm) is irradiated to the surface of the low reflection layer 15, and the reflectance of EUV light is measured. As a result, the reflectance of EUV light is 0.4%, and it is confirmed that the EUV absorption characteristics are excellent.
  • Comparative Example 1 Comparative Example 1 was carried out in the same procedure as in Example 1 except that a single Ru layer was formed as the protective layer 13 on the reflective layer 12 using the ion beam sputtering method.
  • the deposition conditions for the Ru layer are as follows. (Ru layer deposition conditions) Target: Ru target.
  • Sputtering gas Ar gas (gas pressure: 0.02 Pa).
  • -Voltage 700V.
  • Film forming speed 0.052 nm / sec.
  • -Film thickness 3 nm.
  • the surface roughness rms of the protective layer 13 was 0.15 nm.
  • (3) Heat treatment resistance The sample formed up to the protective layer 13 by the above procedure was subjected to heat treatment (atmosphere) at 210 ° C. for 10 minutes. Before and after this treatment, the surface of the protective layer 13 was irradiated with EUV light (wavelength 13.5 nm), and the EUV reflectivity was measured using an EUV reflectometer. The decrease in EUV reflectance before and after this treatment was 7.8%. From this result, it was confirmed that the mask blank of Comparative Example 1 was inferior in heat treatment resistance compared to the mask blank of Example 1.
  • Example 2 In this example, the EUV mirror 2 shown in FIG. 4 was produced.
  • a SiO 2 —TiO 2 glass substrate (outer dimensions 6 inches (152.4 mm) square, thickness 6.3 mm) was used.
  • This glass substrate has a thermal expansion coefficient of 0.2 ⁇ 10 ⁇ 7 / ° C., a Young's modulus of 67 GPa, a Poisson's ratio of 0.17, and a specific rigidity of 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 (not shown) having a sheet resistance of 100 ⁇ / ⁇ was applied to the back surface of the substrate 11 by depositing a Cr film having a thickness of 100 nm using a magnetron sputtering method.
  • a substrate 11 (outer dimensions 6 inches (152.4 mm) square, thickness 6.3 mm) is fixed to a normal electrostatic chuck having a flat plate shape by using the formed Cr film, and ions are formed on the surface of the substrate 11.
  • the Mo / Si multilayer reflective film (reflective layer) having a total film thickness of 340 nm ((2.3 nm + 4.5 nm) ⁇ 50) is obtained by repeating 50 cycles of alternately forming the Mo film and the Si film by using the beam sputtering method. 12) was formed.
  • the uppermost layer of the Mo / Si multilayer reflective film is a Si film.
  • the conditions for forming the Mo film and the Si film are as follows.
  • Mo film formation conditions -Target: Mo target.
  • Sputtering gas Ar gas (gas pressure: 0.02 Pa).
  • Film forming speed 0.064 nm / sec.
  • -Film thickness 2.3 nm.
  • Target Si target (boron doped).
  • Sputtering gas Ar gas (gas pressure: 0.02 Pa).
  • -Voltage 700V.
  • Film forming speed 0.077 nm / sec. -Film thickness: 4.5 nm.
  • a Ru layer was formed as a first layer 13a of the protective layer 13 on the reflective layer 12 by using an ion beam sputtering method.
  • the conditions for forming the first layer 13a are as follows.
  • Target Ru target.
  • Sputtering gas Ar gas (gas pressure: 0.02 Pa).
  • -Voltage 700V.
  • Film forming speed 0.052 nm / sec.
  • -Film thickness 1.25 nm.
  • a Mo layer was formed as the second layer 13b of the protective layer 13 by using an ion beam sputtering method.
  • the conditions for forming the second layer 13b are as follows. -Target: Mo target. Sputtering gas: Ar gas (gas pressure: 0.02 Pa). -Voltage: 700V. Film forming speed: 0.064 nm / sec. -Film thickness: 0.5 nm.
  • a Ru layer was formed as the third layer 13c of the protective layer 13 by ion beam sputtering.
  • the formation conditions of the third layer 13c are as follows.
  • the surface of the protective layer 13 was irradiated with EUV light (wavelength 13.5 nm), and the EUV reflectivity was measured using an EUV reflectometer (MBR (product name) manufactured by AIXUV). The decrease in EUV reflectance before and after this treatment was 5.4%.
  • the decrease in EUV light reflectance due to oxidation of the Ru protective layer is suppressed. Further, by suppressing the progress of the EUV light reflectance over time during EUV exposure, it is not necessary to change the exposure conditions in the middle, and the life of the EUV mask or EUV mirror can be prolonged.
  • the EUV mask produced using the EUV mask blank of the present invention is a highly reliable EUV mask in which the change in EUV light reflectance with time is small during EUV exposure, and is an integrated pattern consisting of fine patterns. Useful for the manufacture of circuits. It should be noted that the entire contents of the specification, claims, drawings and abstract of Japanese Patent Application No. 2009-279401 filed on Dec. 9, 2009 are cited here as disclosure of the specification of the present invention. Incorporated.
  • EUV mask blank 2 EUV mirror 11: Substrate 12: Multilayer reflective film 13: Protective layer 13a: First layer 13b: Second layer 13c: Third layer 14: Absorber layer 15: Low reflective layer

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Abstract

L'invention concerne un élément optique EUV dans lequel la diminution du facteur de réflexion à cause de l'oxydation d'une couche de protection Ru est évitée, ainsi qu'un substrat recouvert d'une couche réfléchissante utilisé dans la fabrication de cet élément optique EUV. Plus spécifiquement, l'invention concerne un substrat recouvert d'une couche réfléchissante pour lithographie EUV, dans lequel, sur le substrat, sont formées dans l'ordre, une couche réfléchissante réfléchissant le rayonnement EUV et une couche de protection protégeant la couche réfléchissante. Ce substrat recouvert d'un film réfléchissant pour lithographie EUV se caractérise en ce que la couche réfléchissante est une couche réfléchissante multicouche Mo/Si et la couche de protection possède une structure multicouche dans laquelle sont stratifiées dans l'ordre, une première couche constituée de Ru ou d'un composé Ru, une deuxième couche constituée de Mo et une troisième couche constituée de Ru ou d'un composé Ru.
PCT/JP2010/072047 2009-12-09 2010-12-08 Élément optique pour lithographie par ultraviolet extrême (euv) Ceased WO2011071086A1 (fr)

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EP10836006.6A EP2511943A4 (fr) 2009-12-09 2010-12-08 Élément optique pour lithographie par ultraviolet extrême (euv)
KR1020127008116A KR20130007533A (ko) 2009-12-09 2010-12-08 Ｅｕｖ 리소그래피용 광학 부재
JP2011545229A JP5590044B2 (ja) 2009-12-09 2010-12-08 Ｅｕｖリソグラフィ用光学部材
US13/472,002 US8986910B2 (en) 2009-12-09 2012-05-15 Optical member for EUV lithography

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JP2009279401 2009-12-09

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JP2015501528A (ja) * 2011-09-27 2015-01-15 カール・ツァイス・エスエムティー・ゲーエムベーハー 安定した組成を有する酸窒化物キャッピング層を備えたｅｕｖミラー、ｅｕｖリソグラフィ装置、及び作動方法
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TW201131284A (en) 2011-09-16
US8986910B2 (en) 2015-03-24
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