WO2011071126A1 - Miroir multicouche pour lithographie par ultraviolets extrêmes et procédé de production associé - Google Patents

Miroir multicouche pour lithographie par ultraviolets extrêmes et procédé de production associé Download PDF

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WO2011071126A1
WO2011071126A1 PCT/JP2010/072169 JP2010072169W WO2011071126A1 WO 2011071126 A1 WO2011071126 A1 WO 2011071126A1 JP 2010072169 W JP2010072169 W JP 2010072169W WO 2011071126 A1 WO2011071126 A1 WO 2011071126A1
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layer
nitrogen
multilayer
protective layer
euvl
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PCT/JP2010/072169
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English (en)
Japanese (ja)
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正樹 三上
光彦 駒木根
生田　順亮
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旭硝子株式会社
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Priority to JP2011545249A priority Critical patent/JP5699938B2/ja
Priority to EP10836046.2A priority patent/EP2511945A4/fr
Publication of WO2011071126A1 publication Critical patent/WO2011071126A1/fr
Priority to US13/443,108 priority patent/US8580465B2/en

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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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G02B1/111—Anti-reflection coatings using layers comprising organic materials
    • 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
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
    • 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
    • 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

Definitions

  • the present invention relates to a multilayer mirror for EUV (Extreme Ultraviolet) lithography (hereinafter referred to as “multilayer mirror for EUVL” in the present specification) and a method for manufacturing the same.
  • EUV Extreme Ultraviolet
  • 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 subsequent 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.
  • a mirror used in EUV light lithography has a structure in which a reflective layer that reflects EUV light is formed on a substrate made of glass or the like.
  • a reflective layer since a high EUV light reflectance can be achieved, a multilayer reflective film in which a high refractive index layer and a low refractive index layer are alternately laminated a plurality of times is usually used. Therefore, a multilayer mirror in which a multilayer reflective film is formed on such a substrate is usually used as a mirror used in EUV photolithography (see Patent Document 1).
  • a protective layer (protective capping layer) is formed on the multilayer reflective film for the purpose of protecting the multilayer reflective film from chemical and physical erosion.
  • the multilayer mirror described in Patent Document 1 includes a protective capping layer made of a material selected from ruthenium (Ru) and rhodium (Rh), and compounds and alloys thereof.
  • the multilayer reflective film of the multilayer mirror for EUVL a Mo / Si multilayer reflective film using a molybdenum (Mo) layer as a low refractive index layer and a silicon (Si) layer as a high refractive index layer is usually used.
  • Mo molybdenum
  • Si silicon
  • Ru is preferably used because a high reflectance is obtained even when the surface of the protective layer is irradiated with EUV light.
  • the Ru protective layer when Ru is used as the material of the protective layer, the Ru protective layer, in the process (for example, cleaning process, heating process, etc.) performed at the time of manufacturing the multilayer mirror, or at the EUV exposure in EUV light lithography, Furthermore, when the uppermost layer of the multilayer reflective film (Si layer in the case of Mo / Si multilayer reflective film) is oxidized, there is a possibility that the EUV light reflectance when the EUV light is irradiated on the surface of the protective layer may be reduced. There is a problem. In particular, since the decrease in EUV light reflectance during EUV exposure progresses with time, it may be necessary to change the exposure conditions in the middle, the need to replace the EUVL multilayer mirror, and the EUVL multilayer film.
  • an object of the present invention is to provide a multilayer mirror for EUVL in which a decrease in EUV light reflectance due to oxidation from a Ru protective layer is suppressed, and a method for manufacturing the same.
  • the inventors of the present invention formed an intermediate layer containing a predetermined amount of nitrogen and Si between the Mo / Si multilayer reflective film and the Ru protective layer. It has been found that a decrease in EUV light reflectance due to oxidation from the protective layer can be suppressed.
  • 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 multilayer mirror for lithography The reflective layer is a Mo / Si multilayer reflective film;
  • the protective layer is a Ru layer or a Ru compound layer;
  • an intermediate layer containing 0.5 to 25 at% nitrogen and 75 to 99.5 at% nitrogen is formed between the reflective layer and the protective layer.
  • a multilayer mirror (multilayer mirror for EUVL) 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 intermediate layer is formed in contact with the Si film.
  • the intermediate layer preferably has a thickness of 0.2 to 2.5 nm.
  • the surface roughness rms of the protective layer surface is preferably 0.5 nm or less.
  • the protective layer preferably has a thickness of 1 to 10 nm.
  • the present invention also provides a method for manufacturing a semiconductor integrated circuit, characterized in that a semiconductor integrated circuit is manufactured by exposing an object to be exposed using the above-described EUVL multilayer film mirror of the present invention.
  • the present invention also provides a multilayer reflective film for EUV lithography by forming a multilayer reflective film that reflects EUV light on a film formation surface of a substrate and then forming a protective layer for the multilayer reflective film on the multilayer reflective film.
  • a method of manufacturing a multilayer mirror for EUVL which manufactures a film mirror (multilayer mirror for EUVL),
  • the multilayer reflective film is a Mo / Si multilayer reflective film
  • the protective layer is a Ru layer or a Ru compound layer; After forming the Mo / Si multilayer reflective film, the surface of the Si layer, which is the uppermost layer of the Mo / Si multilayer reflective film, is exposed to a nitrogen-containing atmosphere without being exposed to the atmosphere, and nitrogen is contained in the Si layer surface.
  • a method for manufacturing a multilayer mirror for EUVL wherein the protective layer is formed after forming the protective layer.
  • the product of the nitrogen partial pressure (Torr) and the exposure time (s) of the nitrogen-containing atmosphere is 1 ⁇ 10 ⁇ 6 Torr ⁇ s or more, The temperature is more preferably 0 to 160 ° C.
  • the product of the nitrogen partial pressure (Torr) and the exposure time (s) of the nitrogen-containing atmosphere is 1 ⁇ 10 ⁇ 6 Torr ⁇ s or more,
  • the temperature is more preferably 0 to 150 ° C.
  • the Si layer surface is exposed to a nitrogen-containing atmosphere, the nitrogen-containing atmosphere is maintained in a plasma state, the Si layer surface is heat-treated, or the Si layer surface is It is preferable to irradiate with ultraviolet rays in order to promote the nitrogen content on the Si layer surface.
  • the multilayer mirror for EUVL of the present invention a decrease in EUV light reflectance due to oxidation from the Ru protective layer is suppressed. Further, according to the manufacturing method of the present invention, it is possible to manufacture a multilayer mirror for EUVL in which a decrease in EUV light reflectance due to oxidation from the Ru protective layer is suppressed. Further, the multilayer mirror for EUV lithography of the present invention suppresses a decrease in EUV light reflectivity, so that it can be effectively used in the manufacture of semiconductor integrated circuits. Particularly, a semiconductor integrated circuit having a fine pattern can be used. Production efficiency is high and can be manufactured.
  • FIG. 1 is a schematic sectional view showing an embodiment of the multilayer mirror for EUVL of the present invention.
  • FIG. 1 is a schematic sectional view showing an embodiment of the multilayer mirror for EUVL of the present invention.
  • a reflective layer 12 that reflects EUV light and a protective layer 14 that protects the reflective layer 12 are formed on a substrate 11 in this order.
  • an intermediate layer 13 containing a predetermined amount of nitrogen and Si described later is formed between the reflective layer 12 and the protective layer 14.
  • the substrate 11 satisfies the characteristics as a substrate for a multilayer mirror for EUVL. 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 a smoothness and resistance to a cleaning liquid used for cleaning the multilayer mirror for EUVL.
  • 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.
  • the substrate 11 preferably has a smooth surface with a surface roughness rms of 0.15 nm or less because a high reflectance can be obtained in the multilayer mirror for EUVL.
  • the size, thickness, and the like of the substrate 11 are appropriately determined based on the design value of the mirror. It is preferable that no defects exist on the surface of the substrate 11 on the side where the multilayer reflective film 12 is formed.
  • the characteristic particularly required for the reflective layer 12 of the multilayer mirror for EUVL is a high EUV light reflectance.
  • 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.
  • the maximum value of the light reflectance near the wavelength of 13.5 nm is preferably 60% or more, and 65% or more. More preferably.
  • a multilayer reflective film in which a high refractive index layer and a low refractive index layer are alternately laminated a plurality of times is widely used.
  • 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 a Mo / Si multilayer reflective film so that it may become desired thickness using well-known 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.
  • an intermediate layer 13 containing 0.5 to 25 at% nitrogen and 75 to 99.5 at% Si is formed between the reflective layer 12 and the protective layer 14.
  • the fall of the EUV light reflectance by the oxidation from a Ru protective layer is suppressed.
  • the reason why the formation of the intermediate layer 13 having the above composition between the reflective layer 12 and the protective layer 14 suppresses the decrease in the EUV light reflectance due to oxidation from the Ru protective layer is considered to be as follows. .
  • the intermediate layer 13 having the above composition nitrogen is added to the intermediate layer 13 in advance so as not to cause a decrease in reflectance due to a large amount of oxygen contained in the uppermost Si film of the reflective layer 12 due to oxidation of the Ru protective layer.
  • the reflectance after film formation is high and the effect of suppressing oxidation is obtained.
  • the Ru protective layer is oxidized during the process (for example, each process such as cleaning, defect inspection, heating process, defect correction, etc.) performed at the time of manufacturing the EUVL multilayer mirror or during EUV exposure in EUV light lithography.
  • the presence of the intermediate layer 13 having the effect of suppressing oxidation causes the Mo / Si multilayer reflective film under the intermediate layer 13 to be oxidized, more specifically. Therefore, it is considered that the uppermost Si layer of the Mo / Si multilayer reflective film is suppressed from being oxidized, and as a result, a decrease in EUV light reflectance due to oxidation from the Ru protective layer is suppressed. It is done.
  • the intermediate layer 13 between the reflective layer 12 (Mo / Si multilayer reflective film) and the protective layer 14 (Ru protective layer) the Mo / Si multilayer reflective film of the Mo / Si multilayer reflective film is formed when the protective layer 14 is formed. It is possible to prevent Si in the uppermost Si layer from diffusing into the Ru protective layer.
  • the intermediate layer 13 having the above composition exposes the Si layer surface, which is the uppermost layer of the Mo / Si multilayer reflective film, to a nitrogen-containing atmosphere. Can be formed.
  • the nitrogen content in the intermediate layer 13 is more than 25 at%, the formation of the protective layer 14 formed on the Si layer, which is the uppermost layer of the Mo / Si multilayer reflective film, or on the intermediate layer 13 is performed.
  • the intermediate layer 13 preferably contains 0.5 to 15 at% nitrogen, 85 to 99.5 at% Si, and contains 0.5 to 10 at% nitrogen from the viewpoint of lowering the EUV light reflectance.
  • Si is contained at 80 to 99.5 at%, nitrogen is contained at 1 to 9 at%, Si is preferably contained at 91 to 99 at%, nitrogen is contained at 3 to 9 at%, and Si is contained at 91 It is even more preferable to contain ⁇ 97 at%, particularly preferable to contain 5 to 8 at% nitrogen and 92 to 95 at% Si.
  • the intermediate layer 13 preferably does not contain fluorine. Further, if carbon or hydrogen is contained in the intermediate layer 13, it may react with oxygen in the intermediate layer 13 to release oxygen in the intermediate layer 13 and deteriorate the structure of the intermediate layer 13. Therefore, it is preferable that the intermediate layer 13 does not contain carbon or hydrogen.
  • the fluorine, carbon, and hydrogen content in the intermediate layer 13 is preferably 3 at% or less, more preferably 1 at% or less, and particularly preferably 0.05 at% or less.
  • the content of Ni, Y, Ti, La, Cr, or Rh in the intermediate layer 13 is preferably 3 at% or less in terms of the total content of these elements, and is 1 at% or less. Is more preferable, and 0.05 at% or less is particularly preferable.
  • the oxygen content in the intermediate layer 13 is also preferably 3 at% or less, and more preferably 1 at% or less.
  • the film thickness of the intermediate layer 13 is preferably 0.2 to 2.5 nm from the viewpoint of suppressing the decrease in EUV light reflectance due to oxidation from the Ru protective layer, and is preferably 0.4 to 2 nm. More preferably, it is 0.5 to 1.5 nm.
  • the thickness of the uppermost Si layer of the multilayer reflective film is preferably 2 to 4.8 nm and is preferably 2.5 to 4.5 nm because the intermediate layer 13 is formed by exposure to a nitrogen-containing atmosphere. More preferably, it is 3.0 to 4 nm.
  • the intermediate layer 13 having the above composition has a nitrogen-containing atmosphere without exposing the surface of the Si layer, which is the uppermost layer of the Mo / Si multilayer reflective film, to the atmosphere after the Mo / Si multilayer reflective film is formed. It can be formed by lightly nitriding the surface of the Si layer by exposing to, that is, incorporating nitrogen into the surface of the Si layer.
  • the nitrogen-containing atmosphere in this specification means a nitrogen gas atmosphere or a mixed gas atmosphere of nitrogen gas and an inert gas such as argon.
  • the nitrogen gas concentration in the atmosphere is preferably 20 vol% or more, more preferably 50 vol% or more, and further preferably 80 vol% or more.
  • the surface of the Si layer which is the uppermost layer of the Mo / Si multilayer reflective film, is exposed to a nitrogen-containing atmosphere without being exposed to the atmosphere. If the surface of the Si layer is exposed to the atmosphere before exposure, the surface of the Si layer is oxidized. After that, even if the surface of the Si layer is exposed to nitrogen, nitridation of the surface of the Si layer causes nitrogen to be added to the surface of the Si layer. This is because the intermediate layer 13 containing nitrogen and Si may not be able to be formed.
  • the nitrogen partial pressure is expressed in Pa
  • the product of the nitrogen partial pressure (Pa) and the exposure time (s) in the nitrogen-containing atmosphere is 1.33 ⁇ 10 ⁇ 4 Pa ⁇ s or more.
  • the product of the nitrogen partial pressure and the exposure time is an index indicating the frequency with which nitrogen in the nitrogen-containing atmosphere collides with the surface of the Si layer, and may hereinafter be referred to as “nitrogen exposure amount” in the present specification.
  • This value is preferably 1 ⁇ 10 ⁇ 6 Torr ⁇ s or more (1.33 ⁇ 10 ⁇ 4 Pa ⁇ s or more) in order to form the intermediate layer 13 having the above composition by nitriding of the Si layer surface.
  • X10 ⁇ 3 Torr ⁇ s or more (1.33 ⁇ 10 ⁇ 1 Pa ⁇ s or more) is more preferable, and 1 ⁇ 10 ⁇ 2 Torr ⁇ s or more (1.33 Pa ⁇ s or more) is further achieved.
  • it is 1 ⁇ 10 ⁇ 1 Torr ⁇ s or more (13.3 Pa ⁇ s or more).
  • the product of the nitrogen partial pressure and the exposure time is preferably 1000 Torr ⁇ s or less.
  • the nitrogen partial pressure in the nitrogen-containing atmosphere that exposes the surface of the Si layer is preferably 1 ⁇ 10 ⁇ 4 Torr to 820 Torr (1.33 ⁇ 10 ⁇ 2 Pa to 109.32 kPa).
  • the nitrogen partial pressure indicates the atmospheric pressure of the nitrogen gas atmosphere.
  • the oxygen concentration in the nitrogen-containing atmosphere that exposes the Si layer surface is extremely low.
  • the nitrogen partial pressure in the nitrogen-containing atmosphere is 1 ⁇ 10 ⁇ 4 Torr to 820 Torr (1.33 ⁇ 10 ⁇ 2 Pa to 109.32 kPa).
  • the oxygen partial pressure in the atmosphere is preferably 1 ⁇ 10 ⁇ 6 Torr (1.33 ⁇ 10 ⁇ 4 Pa) or less.
  • the concentration of a gas component composed of a compound containing O 3 , H 2 O and OH groups in a nitrogen-containing atmosphere that exposes the surface of the Si layer is also extremely low.
  • the nitrogen partial pressure in the nitrogen-containing atmosphere is in the above range, that is, the nitrogen partial pressure in the nitrogen-containing atmosphere is 1 ⁇ 10 ⁇ 4 Torr to 820 Torr (1.33 ⁇ 10 ⁇ 2 Pa to 109.32 kPa).
  • the partial pressure of the gas component composed of the compound containing O 3 , H 2 O, and OH group in the atmosphere is 1 ⁇ 10 ⁇ 6 Torr (1.33 ⁇ 10 ⁇ 4 Pa) or less.
  • the concentration of F 2 is also very low in nitrogen-containing atmosphere.
  • the nitrogen partial pressure in the nitrogen-containing atmosphere is in the above range, that is, the nitrogen partial pressure in the nitrogen-containing atmosphere is 1 ⁇ 10 ⁇ 4 Torr to 820 Torr (1.33 ⁇ 10 ⁇ 2 Pa to 109.32 kPa).
  • the partial pressure of F 2 in the atmosphere is preferably 1 ⁇ 10 ⁇ 6 Torr (1.33 ⁇ 10 ⁇ 4 Pa) or less.
  • the temperature of the nitrogen-containing atmosphere that exposes the surface of the Si layer is preferably 0 to 170 ° C. If the temperature of the nitrogen-containing atmosphere is less than 0 ° C., there may be a problem of influence due to adsorption of residual moisture in vacuum. If the temperature of the nitrogen-containing atmosphere exceeds 170 ° C., the nitridation of the Si layer proceeds excessively, and the EUV light reflectance of the Mo / Si multilayer reflective film may be lowered.
  • the temperature of the nitrogen-containing atmosphere is more preferably 10 to 160 ° C., and further preferably 20 to 150 ° C., 20 to 140 ° C., and 20 to 120 ° C.
  • the surface of the Si layer when the surface of the Si layer is exposed to a nitrogen-containing atmosphere, the surface of the Si layer may be heat-treated in the above temperature range.
  • the protective layer 14 (Ru protective layer)
  • the intermediate layer 13 is formed by exposing the surface of the Si layer, which is the uppermost layer of the Mo / Si multilayer reflective film, to an atmosphere containing nitrogen. This is preferable because the EUV light reflectance is not lowered and the oxidation durability can be improved.
  • the time for exposing the Si layer surface to the nitrogen-containing atmosphere is set to 600 sec and 6000 sec, respectively.
  • the time for exposing the Si layer surface to the nitrogen-containing atmosphere is not limited to this, and the nitrogen described above is used. It can select suitably in the range which satisfy
  • the surface of the Si layer which is the uppermost layer of the Mo / Si multilayer reflective film, is exposed to nitrogen without being exposed to the atmosphere.
  • the intermediate layer 13 may be formed by heat treatment in the nitrogen-containing atmosphere.
  • the Si layer surface is heat-treated, so that the Si layer surface is nitrided, that is, the nitrogen is applied to the Si layer surface. Inclusion is promoted.
  • the substrate in which the Mo / Si multilayer reflective film is formed is held in the deposition chamber in which the Si layer is formed or in a chamber adjacent to the deposition chamber, and the gas in the chamber is replaced with nitrogen gas.
  • nitrogen gas Or a mixed gas of nitrogen gas and inert gas such as argon
  • the heat treatment temperature when the surface of the Si layer is heat-treated in a nitrogen-containing atmosphere is preferably 120 to 160 ° C., particularly preferably 130 to 150 ° C.
  • the procedure for exposing the Si layer surface to nitrogen gas or a mixed gas of nitrogen gas and an inert gas such as argon under a reduced pressure atmosphere as in the procedures shown in Examples 1 to 4 is the formation of a multilayer reflective film.
  • the step of exposing the surface of the Si layer to nitrogen gas (or a mixed gas of nitrogen gas and an inert gas such as argon) when the protective layer is formed using the same chamber is a preferable procedure.
  • this procedure can control the nitrogen content of the intermediate layer 13 by controlling the exposure amount of nitrogen gas (or a mixed gas of nitrogen gas and inert gas such as argon) to the surface of the Si layer. But it is a preferred procedure.
  • the surface of the Si layer which is the uppermost layer of the Mo / Si multilayer reflective film, is exposed to the nitrogen without being exposed to the atmosphere.
  • the nitridation of the Si layer surface that is, the inclusion of nitrogen in the Si layer surface
  • the reduced pressure atmosphere can be maintained in a plasma state by nitriding the Si layer surface, that is, the Si layer. This is preferable for promoting nitrogen content on the surface.
  • the Si layer surface when the Si layer surface is exposed to nitrogen gas or a mixed gas of nitrogen gas and an inert gas such as argon in a reduced pressure atmosphere, the Si layer surface may be irradiated with ultraviolet rays in the reduced pressure atmosphere. It is preferable for promoting surface nitriding, that is, nitrogen content on the Si layer surface.
  • the Si layer surface after the Mo / Si multilayer reflective film is formed, the Si layer surface, which is the uppermost layer of the Mo / Si multilayer reflective film, is exposed to a nitrogen-containing atmosphere without being exposed to the atmosphere.
  • the nitrogen-containing pressure atmosphere is a reduced pressure atmosphere.
  • the pressure in the reduced pressure atmosphere is preferably 0.01 to 0.5 mTorr, and more preferably 0.1 to 0.5 mTorr.
  • the temperature of the reduced-pressure atmosphere is more preferably 0 to 170 ° C.
  • the protective layer 14 is provided for the purpose of protecting the reflective layer 12 from chemical and physical erosion. For EUVL multilayer mirrors, this is done to damage the reflective layer 12 due to a cleaning process using ozone water or the like performed after manufacturing the EUVL multilayer mirror, or to increase productivity in an exposure machine held in a vacuum. In order to prevent damage to the reflection layer 12 due to the prolonged irradiation of EUV light, damage to the reflection layer 12 due to cleaning performed for the purpose of removing carbon contamination on the surface of the EUVL multilayer mirror, A protective layer is formed on layer 12. Therefore, the material of the protective layer 14 is selected from the viewpoint of preventing damage to the reflective layer 12.
  • the protective layer 14 itself preferably has a high EUV light reflectance so that the EUV light reflectance in the reflective layer 12 is not impaired even after the protective layer 14 is formed.
  • a Ru layer, a Ru compound layer, or the like is formed as the protective layer 14.
  • Such a Ru compound is preferably at least one selected from the group consisting of RuB, RuNb and RuZr.
  • the Ru content is preferably 50 at% or more, more preferably 80 at% or more, and particularly preferably 90 at% or more.
  • the protective layer 14 is a RuNb layer
  • the Nb content in the protective layer 14 is preferably 5 to 40 at%. More preferably, it is 5 to 30 at%.
  • the surface roughness rms on the surface of the protective layer 14 is preferably 0.5 nm or less.
  • the surface roughness rms of 0.5 nm or less means that the surface roughness of the root mean square is 0.5 nm or less.
  • the EUV light reflectance decreases. If the surface roughness rms of the surface of the protective layer 14 is 0.5 nm or less, the EUV light reflectance can be increased, which is preferable.
  • the surface roughness rms of the surface of the protective layer 14 is more preferably 0.4 nm or less, and further preferably 0.3 nm or less.
  • the thickness of the protective layer 14 is preferably 1 to 10 nm because the EUV light reflectance can be increased.
  • the thickness of the protective layer 14 is more preferably 1 to 5 nm, and further preferably 2 to 4 nm.
  • the protective layer 14 can be formed using a known film formation method such as a magnetron sputtering method or an ion beam sputtering method.
  • a Ru layer is formed as the protective layer 14 using an ion beam sputtering method
  • a 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.
  • the decrease in EUV light reflectance before and after cleaning is 0.9% or less. It is preferable that it is 0.5% or less.
  • the decrease in EUV light reflectance before and after the heat treatment is 7% or less. % Or less is more preferable.
  • the value of the fall of the EUV light reflectance before and behind heat processing is large compared with the fall of the EUV light reflectance before and behind ozone water washing
  • a method for manufacturing a semiconductor integrated circuit using the multilayer mirror for EUVL according to the present invention will be described.
  • 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 a reflective photomask is installed in the reflective exposure apparatus using the above-described EUVL multilayer mirror as a reflective mirror.
  • the EUV light is irradiated from the light source to the photomask through the reflecting mirror, and the EUV light is reflected by the photomask 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 the EUVL multilayer mirror 1 shown in FIG. 1 was produced.
  • a SiO 2 —TiO 2 glass substrate was used as the substrate 11 for film formation.
  • 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.
  • the film forming conditions for the Mo layer and the Si layer are as follows.
  • Mo layer deposition conditions Mo target-Sputtering gas: Ar gas (gas pressure: 0.02 Pa) ⁇ Voltage: 700V ⁇ Deposition rate: 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 ⁇ Deposition rate: 0.077 nm / sec ⁇ Film thickness: 4.5nm
  • a Ru layer as the protective layer 14 was formed by using an ion beam sputtering method.
  • the formation conditions of the protective layer 14 are as follows. ⁇ Target: Ru target ⁇ Sputtering gas: Ar gas (gas pressure: 0.02 Pa) ⁇ Voltage: 700V ⁇ Deposition rate: 0.052 nm / sec ⁇ Film thickness: 2.5nm
  • (1) Film composition The composition in the depth direction from the surface of the protective layer 14 to the reflective layer (Mo / Si multilayer reflective film) 12 is measured using an X-ray photoelectron spectrometer (manufactured by ULVAC-PHI, Inc .: Quantera). It was confirmed that the intermediate layer 13 was formed between the Si layer, which is the uppermost layer of the Mo / Si multilayer reflective film, and the protective layer 14 by measuring using SXM).
  • the composition of the intermediate layer 13 was 6 at% nitrogen and 94 at% Si.
  • the film thickness of the intermediate layer 13 was 1 nm.
  • the surface roughness of the protective layer 14 was confirmed using an atomic force microscope (manufactured by Seiko Instruments Inc .: No. SPI3800) according to JIS-B0601 (1994). The surface roughness rms of the protective layer 14 was 0.15 nm.
  • (3) Cleaning resistance The surface of the protective layer 14 was treated by spin cleaning with ozone water for a total of 600 seconds. Before and after this treatment, the surface of the protective layer 14 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 0.5%.
  • Heat treatment resistance The EUVL multilayer mirror was heat-treated at 210 ° C. for 10 minutes (in air). The decrease in EUV reflectance before and after this treatment was 4.1%.
  • (1) Film composition The composition in the depth direction from the surface of the protective layer 14 to the reflective layer (Mo / Si multilayer reflective film) 12 is measured using an X-ray photoelectron spectrometer (manufactured by ULVAC-PHI, Inc .: Quantera). It was confirmed that the intermediate layer 13 was formed between the Si layer, which is the uppermost layer of the Mo / Si multilayer reflective film, and the protective layer 14 by measuring using SXM).
  • the composition of the intermediate layer 13 was 8 at% nitrogen and 92 at% Si.
  • the film thickness of the intermediate layer 13 was 1 nm.
  • the surface roughness of the protective layer 14 was confirmed using an atomic force microscope (manufactured by Seiko Instruments Inc .: No. SPI3800) according to JIS-B0601 (1994). The surface roughness rms of the protective layer 14 was 0.15 nm.
  • (3) Cleaning resistance The surface of the protective layer 14 was treated by spin cleaning with ozone water for a total of 600 seconds. Before and after this treatment, the surface of the protective layer 14 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 0.3%.
  • Heat treatment resistance The EUVL multilayer mirror is heated at 210 ° C. for 10 minutes (in air). The decrease in EUV reflectivity before and after this treatment is 3.7%.
  • Example 3 is the same as Example 1 except that heat treatment was performed under the following exposure conditions (without RF discharge) instead of exposure to the nitrogen-containing atmosphere (nitrogen and argon mixed gas atmosphere) on the surface of the Si layer. The procedure of was carried out. After the formation of the Mo / Si multilayer reflective film, the uppermost Si layer surface of the Mo / Si multilayer reflective film is placed in a nitrogen-containing atmosphere (a mixed gas atmosphere of nitrogen and argon) according to the following conditions. Heat treatment). (Exposure conditions) Atmospheric gas: Ar gas (carrier gas), flow rate 17 sccm.
  • the following evaluation is performed on the multilayer mirror for EUVL obtained by the above procedure.
  • (1) Film composition The composition in the depth direction from the surface of the protective layer 14 to the reflective layer (Mo / Si multilayer reflective film) 12 is measured using an X-ray photoelectron spectrometer (manufactured by ULVAC-PHI, Inc .: Quantera). By measuring using SXM), it is confirmed that the intermediate layer 13 is formed between the Si layer which is the uppermost layer of the Mo / Si multilayer reflective film and the protective layer 14.
  • the composition of the intermediate layer 13 is 6 at% nitrogen and 94 at% Si. Further, the film thickness of the intermediate layer 13 is 1 nm.
  • the surface roughness of the protective layer 14 is confirmed using an atomic force microscope (manufactured by Seiko Instruments Inc .: No. SPI3800) according to JIS-B0601 (1994). The surface roughness rms of the protective layer 14 is 0.15 nm.
  • (3) Cleaning resistance The surface of the protective layer 14 is treated for a total of 600 seconds by spin cleaning with ozone water. Before and after this treatment, the surface of the protective layer 14 is irradiated with EUV light (wavelength 13.5 nm), and the EUV reflectivity is measured using an EUV reflectometer (MBR (product name) manufactured by AIXUV). The decrease in EUV reflectance before and after this treatment is 0.5%.
  • Heat treatment resistance The EUVL multilayer mirror is heated at 210 ° C. for 10 minutes (in air). The decrease in EUV reflectivity before and after this treatment is 4.3%.
  • Example 4 In Example 4, the same procedure as in Example 3 is performed except that the heat treatment conditions in a nitrogen-containing atmosphere (in a mixed gas atmosphere of nitrogen and argon) are as follows. (Heat treatment conditions) Atmospheric gas: Ar gas (carrier gas), flow rate 17 sccm.
  • the following evaluation is performed on the multilayer mirror for EUVL obtained by the above procedure.
  • (1) Film composition The composition in the depth direction from the surface of the protective layer 14 to the reflective layer (Mo / Si multilayer reflective film) 12 is measured using an X-ray photoelectron spectrometer (manufactured by ULVAC-PHI, Inc .: Quantera). By measuring using SXM), it is confirmed that the intermediate layer 13 is formed between the Si layer which is the uppermost layer of the Mo / Si multilayer reflective film and the protective layer 14.
  • the composition of the intermediate layer 13 is 8 at% nitrogen and 92 at% Si. Further, the film thickness of the intermediate layer 13 is 1 nm.
  • the surface roughness of the protective layer 14 is confirmed using an atomic force microscope (manufactured by Seiko Instruments Inc .: No. SPI3800) according to JIS-B0601 (1994). The surface roughness rms of the protective layer 14 is 0.15 nm.
  • (3) Cleaning resistance The surface of the protective layer 14 is treated for a total of 600 seconds by spin cleaning with ozone water. Before and after this treatment, the surface of the protective layer 14 is irradiated with EUV light (wavelength 13.5 nm), and the EUV reflectivity is measured using an EUV reflectometer (MBR (product name) manufactured by AIXUV). The decrease in EUV reflectivity before and after this treatment is 0.3%.
  • Heat treatment resistance The EUVL multilayer mirror is heated at 210 ° C. for 10 minutes (in air). The decrease in EUV reflectivity before and after this treatment is 3.7%.
  • Comparative Example 1 In Comparative Example 1, after forming the reflective layer (Mo / Si multilayer reflective film) 12, the protective layer 14 was formed without exposing the Si layer, which is the uppermost layer of the Mo / Si multilayer reflective film, to the nitrogen-containing atmosphere. was carried out in the same procedure as in Example 1.
  • (1) Film composition The composition in the depth direction from the surface of the protective layer 14 to the reflective layer (Mo / Si multilayer reflective film) 12 is measured using an X-ray photoelectron spectrometer (manufactured by ULVAC-PHI, Inc .: Quantera). SXM), the formation of the intermediate layer 13 is not confirmed between the Si layer, which is the uppermost layer of the Mo / Si multilayer reflective film, and the protective layer 14, and the lamination of the Si layer and the protective layer 14 is confirmed.
  • the nitrogen content in the body was 0%.
  • the surface roughness of the protective layer 14 was confirmed using an atomic force microscope (manufactured by Seiko Instruments Inc .: No. SPI3800) according to JIS-B0601 (1994). The surface roughness rms of the protective layer 14 was 0.15 nm. (3) Cleaning resistance The surface of the protective layer 14 was treated by spin cleaning with ozone water for a total of 600 seconds. Before and after this treatment, the surface of the protective layer 14 was irradiated with EUV light (wavelength 13.5 nm), and the EUV reflectivity was measured using an EUV reflectometer. The decrease in EUV reflectivity before and after this treatment was 2.1%.
  • Comparative Example 2 Comparative Example 2 was carried out in the same procedure as Example 1 except that the surface of the Si layer was exposed to an Ar gas atmosphere under the following exposure conditions instead of the nitrogen-containing atmosphere.
  • Exposure conditions ⁇ Exposure gas: Ar gas, flow rate 17sccm (Ar gas is supplied during RF discharge) ⁇ Atmospheric pressure: 0.1 mTorr (1.3 ⁇ 10 ⁇ 2 Pa) ⁇ Atmosphere temperature: 20 °C ⁇ Exposure time: 600 sec ⁇ RF discharge frequency: 1.8 MHz ⁇ RF power: 500W
  • (1) Film composition The composition in the depth direction from the surface of the protective layer 14 to the reflective layer (Mo / Si multilayer reflective film) 12 is measured using an X-ray photoelectron spectrometer (manufactured by ULVAC-PHI, Inc .: Quantera). SXM), the formation of the intermediate layer 13 is not confirmed between the Si layer, which is the uppermost layer of the Mo / Si multilayer reflective film, and the protective layer 14, and the lamination of the Si layer and the protective layer 14 is confirmed.
  • the nitrogen content in the body was 0%.
  • the surface roughness of the protective layer 14 was confirmed using an atomic force microscope (manufactured by Seiko Instruments Inc .: No. SPI3800) according to JIS-B0601 (1994). The surface roughness rms of the protective layer 14 was 0.15 nm. (3) Cleaning resistance The surface of the protective layer 14 was treated by spin cleaning with ozone water for a total of 600 seconds. Before and after this treatment, the surface of the protective layer 14 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 2.9%.
  • Comparative Example 3 In Comparative Example 3, the same procedure as in Example 1 is performed except that the surface of the Si layer is not subjected to heat treatment or RF discharge and is exposed under the following exposure conditions. After the formation of the Mo / Si multilayer reflective film, the uppermost Si layer surface of the Mo / Si multilayer reflective film is placed in a nitrogen-containing atmosphere (a mixed gas atmosphere of nitrogen and argon) according to the following conditions. Middle). (Exposure conditions) Atmospheric gas: Ar gas (carrier gas), flow rate 17 sccm.
  • a nitrogen-containing atmosphere a mixed gas atmosphere of nitrogen and argon
  • Nitrogen gas, flow rate 50sccm Nitrogen gas partial pressure: 0.2 mTorr (2.6 ⁇ 10 ⁇ 2 Pa) ⁇ Atmospheric pressure: 0.3 mTorr (3.5 ⁇ 10 ⁇ 2 Pa) ⁇ Heat treatment temperature: 20 °C ⁇ Heat treatment time: 600 sec
  • the following evaluation is performed on the multilayer mirror for EUVL obtained by the above procedure.
  • (1) Film composition The composition in the depth direction from the surface of the protective layer 14 to the reflective layer (Mo / Si multilayer reflective film) 12 is measured using an X-ray photoelectron spectrometer (manufactured by ULVAC-PHI, Inc .: Quantera). SXM), the formation of the intermediate layer 13 is not confirmed between the Si layer, which is the uppermost layer of the Mo / Si multilayer reflective film, and the protective layer 14, and the lamination of the Si layer and the protective layer 14 is confirmed.
  • the nitrogen content in the body is 0.2%.
  • the surface roughness of the protective layer 14 is confirmed using an atomic force microscope (manufactured by Seiko Instruments Inc .: No. SPI3800) according to JIS-B0601 (1994). The surface roughness rms of the protective layer 14 is 0.15 nm. (3) Cleaning resistance The surface of the protective layer 14 is treated for a total of 600 seconds by spin cleaning with ozone water. Before and after this treatment, the surface of the protective layer 14 is irradiated with EUV light (wavelength 13.5 nm), and the EUV reflectivity is measured using an EUV reflectometer (MBR (product name) manufactured by AIXUV). The decrease in EUV reflectivity before and after this treatment is 1.9%.
  • Comparative Example 4 was performed in the same procedure as Example 3 except that heat treatment was performed in an Ar gas atmosphere according to the following conditions instead of heat treatment of the Si layer surface in a nitrogen-containing atmosphere.
  • Heat treatment conditions ⁇ Atmospheric gas: Ar gas, flow rate 17sccm ⁇ Atmospheric pressure: 0.1 mTorr (1.3 ⁇ 10 ⁇ 2 Pa) ⁇ Heat treatment temperature: 140 °C ⁇ Heat treatment time: 600 sec
  • the following evaluation is performed on the multilayer mirror for EUVL obtained by the above procedure.
  • (1) Film composition The composition in the depth direction from the surface of the protective layer 14 to the reflective layer (Mo / Si multilayer reflective film) 12 is measured using an X-ray photoelectron spectrometer (manufactured by ULVAC-PHI, Inc .: Quantera). SXM), the formation of the intermediate layer 13 is not confirmed between the Si layer, which is the uppermost layer of the Mo / Si multilayer reflective film, and the protective layer 14, and the lamination of the Si layer and the protective layer 14 is confirmed.
  • the nitrogen content in the body is 0%.
  • the surface roughness of the protective layer 14 is confirmed using an atomic force microscope (manufactured by Seiko Instruments Inc .: No. SPI3800) according to JIS-B0601 (1994). The surface roughness rms of the protective layer 14 is 0.15 nm. (3) Cleaning resistance The surface of the protective layer 14 is treated for a total of 600 seconds by spin cleaning with ozone water. Before and after this treatment, the surface of the protective layer 14 is irradiated with EUV light (wavelength 13.5 nm), and the EUV reflectivity is measured using an EUV reflectometer (MBR (product name) manufactured by AIXUV). The decrease in EUV reflectivity before and after this treatment is 2.9%.
  • Comparative Example 5 In Comparative Example 5, the same procedure as in Example 3 is performed except that the Si layer surface is exposed to the air before being heat-treated in a nitrogen-containing atmosphere (in a mixed gas atmosphere of nitrogen and argon).
  • Air exposure conditions Exposed gas: Air (N 2 : about 78% by volume, O 2 : about 21% by volume)
  • Atmospheric pressure 760 Torr (1.0 ⁇ 10 5 Pa)
  • Atmosphere temperature 20 °C ⁇
  • Exposure time 600 sec
  • Atmospheric gas Ar gas (carrier gas), flow rate 17 sccm.
  • the following evaluation is performed on the multilayer mirror for EUVL obtained by the above procedure.
  • (1) Film composition The composition in the depth direction from the surface of the protective layer 14 to the reflective layer (Mo / Si multilayer reflective film) 12 is measured using an X-ray photoelectron spectrometer (manufactured by ULVAC-PHI, Inc .: Quantera). By measuring using SXM), it is confirmed that the intermediate layer 13 is formed between the Si layer which is the uppermost layer of the Mo / Si multilayer reflective film and the protective layer 14.
  • the composition of the intermediate layer 13 is 4 at% oxygen, 1 at% nitrogen, and 95 at% Si. Further, the film thickness of the intermediate layer 13 is 1 nm.
  • the surface roughness of the protective layer 14 is confirmed using an atomic force microscope (manufactured by Seiko Instruments Inc .: No. SPI3800) according to JIS-B0601 (1994). The surface roughness rms of the protective layer 14 is 0.15 nm. (3) Cleaning resistance The surface of the protective layer 14 is treated for a total of 600 seconds by spin cleaning with ozone water. Before and after this treatment, the surface of the protective layer 14 is irradiated with EUV light (wavelength 13.5 nm), and the EUV reflectivity is measured using an EUV reflectometer (MBR (product name) manufactured by AIXUV). The decrease in EUV reflectivity before and after this treatment is 0.8%.
  • the EUVL multilayer mirror of Comparative Example 5 has improved cleaning resistance compared to Comparative Example 1, but it may be inferior to the EUVL multilayer mirrors of Examples 1 to 4 in cleaning resistance. It is confirmed.
  • (4) Heat treatment resistance The EUVL multilayer mirror is heated at 210 ° C. for 10 minutes (in air). The decrease in EUV reflectance before and after this treatment is 8.1%. From this result, it is confirmed that the EUVL multilayer mirror of Comparative Example 5 is inferior in heat treatment resistance to the EUVL multilayer mirrors of Examples 1 to 4.
  • Example 5 when the Si layer as the uppermost layer of the Mo / Si multilayer reflective film was exposed to a nitrogen-containing atmosphere (mixed gas atmosphere of nitrogen and argon), RF discharge was not performed according to the following conditions: The same procedure as in Example 1 was performed except that the surface of the Si layer was irradiated with ultraviolet rays.
  • a nitrogen-containing atmosphere mixed gas atmosphere of nitrogen and argon
  • (1) Film composition The composition in the depth direction from the surface of the protective layer 14 to the reflective layer (Mo / Si multilayer reflective film) 12 is measured using an X-ray photoelectron spectrometer (manufactured by ULVAC-PHI, Inc .: Quantera). It was confirmed that the intermediate layer 13 was formed between the Si layer, which is the uppermost layer of the Mo / Si multilayer reflective film, and the protective layer 14 by measuring using SXM).
  • the composition of the intermediate layer 13 was 8 at% nitrogen and 92 at% Si.
  • the film thickness of the intermediate layer 13 was 1 nm.
  • the surface roughness of the protective layer 14 was confirmed using an atomic force microscope (manufactured by Seiko Instruments Inc .: No. SPI3800) according to JIS-B0601 (1994). The surface roughness rms of the protective layer 14 was 0.15 nm.
  • (3) Cleaning resistance The surface of the protective layer 14 was treated by spin cleaning with ozone water for a total of 600 seconds. Before and after this treatment, the surface of the protective layer 14 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 0.3%.
  • Heat treatment resistance The EUVL multilayer mirror is heated at 210 ° C. for 10 minutes (in air). The decrease in EUV reflectivity before and after this treatment is 3.7%.
  • the multilayer mirror for EUV lithography suppresses a decrease in EUV light reflectivity, so that it can be effectively used in the manufacture of semiconductor integrated circuits. Particularly, a semiconductor integrated circuit having a fine pattern can be produced efficiently. High and can be manufactured.
  • EUVL multilayer mirror 11 Substrate 12: Reflective layer 13: Intermediate layer 14: Protective layer

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Abstract

La présente invention a trait à un miroir multicouche pour lithographie par ultraviolets extrêmes permettant d'empêcher toute réduction du pouvoir de réflexion causée par l'oxydation se produisant à partir de la couche de protection de Ru, et a trait à son procédé de production. Le miroir multicouche selon la présente invention pour lithographie par ultraviolets extrêmes est pourvu d'une couche réfléchissante permettant de réfléchir les rayonnements ultraviolets extrêmes et d'une couche de protection permettant de protéger la couche réfléchissante qui sont formées sur un substrat dans l'ordre susmentionné. Le miroir multicouche est caractérisé en ce que : la couche réfléchissante est un film réfléchissant multicouche de Mo/Si ; la couche de protection est une couche de Ru ou une couche de composé de Ru ; et une couche intermédiaire contenant de 0,5 % à 25 % par atome d'azote et de 75 % à 99,5 % par atome de Si est formée entre la couche réfléchissante et la couche de protection.
PCT/JP2010/072169 2009-12-09 2010-12-09 Miroir multicouche pour lithographie par ultraviolets extrêmes et procédé de production associé WO2011071126A1 (fr)

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JP2011545249A JP5699938B2 (ja) 2009-12-09 2010-12-09 Ｅｕｖリソグラフィ用多層膜ミラーおよびその製造方法
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WO2015012151A1 (fr) * 2013-07-22 2015-01-29 Hoya株式会社 Substrat à film réfléchissant multicouche, ébauche de masque réfléchissant pour lithographie euv, masque réfléchissant pour lithographie euv, son procédé de fabrication et procédé de fabrication de dispositif à semi-conducteurs
WO2015037564A1 (fr) * 2013-09-11 2015-03-19 Hoya株式会社 Substrat ayant un film réfléchissant multicouche, ébauche de masque réfléchissant pour lithographie euv, masque réfléchissant pour lithographie euv, procédé de fabrication de masque réfléchissant pour lithographie euv, et procédé de fabrication de dispositif à semi-conducteurs
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KR101699574B1 (ko) 2017-01-24
CN102687071B (zh) 2013-12-11
KR20120106735A (ko) 2012-09-26
US20120196208A1 (en) 2012-08-02
JP5673555B2 (ja) 2015-02-18
US8993201B2 (en) 2015-03-31
US20120231378A1 (en) 2012-09-13
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