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WO2011071123A1 - Substrat équipé d'une couche réfléchissante pour lithographie par ultraviolets extrêmes, ébauche de masque réfléchissant pour lithographie par ultraviolets extrêmes, masque réfléchissant pour lithographie par ultraviolets extrêmes et processus de production de substrat équipé d'une couche réfléchissante - Google Patents

Substrat équipé d'une couche réfléchissante pour lithographie par ultraviolets extrêmes, ébauche de masque réfléchissant pour lithographie par ultraviolets extrêmes, masque réfléchissant pour lithographie par ultraviolets extrêmes et processus de production de substrat équipé d'une couche réfléchissante Download PDF

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Publication number
WO2011071123A1
WO2011071123A1 PCT/JP2010/072161 JP2010072161W WO2011071123A1 WO 2011071123 A1 WO2011071123 A1 WO 2011071123A1 JP 2010072161 W JP2010072161 W JP 2010072161W WO 2011071123 A1 WO2011071123 A1 WO 2011071123A1
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WIPO (PCT)
Prior art keywords
layer
reflective
nitrogen
protective layer
euv
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Ceased
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PCT/JP2010/072161
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English (en)
Japanese (ja)
Inventor
正樹 三上
光彦 駒木根
生田　順亮
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AGC Inc
Original Assignee
Asahi Glass Co Ltd
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Filing date
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Application filed by Asahi Glass Co Ltd filed Critical Asahi Glass Co Ltd
Priority to KR1020127012513A priority Critical patent/KR101699574B1/ko
Priority to CN2010800562668A priority patent/CN102687071B/zh
Priority to EP10836043.9A priority patent/EP2511944A4/fr
Priority to JP2011545247A priority patent/JP5673555B2/ja
Publication of WO2011071123A1 publication Critical patent/WO2011071123A1/fr
Priority to US13/478,532 priority patent/US8993201B2/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • H10P76/2041—
    • 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 is an EUV (Extreme Ultraviolet: hereinafter referred to as EUV) used for semiconductor manufacturing or the like, a substrate with a reflective layer for lithography, a reflective mask blank for EUV lithography (hereinafter also referred to as “EUV mask blank”). ), A reflective mask for EUV lithography (hereinafter also referred to as “EUV mask”) obtained by patterning the EUV mask blank, a method for manufacturing the substrate with a reflective layer, and a semiconductor integrated circuit using the EUV mask Regarding the method.
  • EUV Extreme Ultraviolet: hereinafter referred to as EUV
  • EUV mask blank A reflective mask 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 that of 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 index layer
  • a silicon (Si) layer which is a high refractive index layer
  • Mo / Si multilayer reflective film with an increased resistance 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.
  • a protective layer is usually formed between the reflective layer and the absorber layer.
  • the protective layer is provided for the purpose of protecting the reflective layer so that the reflective layer is not damaged by an etching process performed for the purpose of patterning the absorber layer.
  • 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.
  • JP 2002-122981 A (US Pat. No. 6,699,625) JP 2005-268750 A
  • the protective layer When Ru is used as the material for the protective layer, a high etching selectivity with respect to the absorber layer can be obtained, and even when the protective layer is formed on the reflective layer, a high etching selectivity is obtained when the protective layer surface is irradiated with EUV light. Reflectance is obtained.
  • the steps performed when manufacturing the mask blank and the steps performed when manufacturing the photomask from the mask blank for example, cleaning, defect inspection, heating step, dry etching
  • the protective layer is oxidized by oxidizing the Ru protective layer and further the uppermost layer of the multilayer reflective film (in the case of a Mo / Si multilayer reflective film).
  • the EUV light reflectance may be reduced when the surface is irradiated with EUV light.
  • the decrease in the EUV light reflectivity during EUV exposure progresses with time, so that it is necessary to change the exposure conditions in the middle of the process, or the life of the photomask is shortened.
  • processes performed when manufacturing a mask blank and processes performed when manufacturing a photomask from the mask blank for example, cleaning, defect inspection, heating process, dry etching, defect correction processes
  • the Ru protective layer, and further, the uppermost layer of the multilayer reflective film is oxidized to reduce the EUV light reflectance when the protective layer surface is irradiated with EUV light. It may be simply referred to as “decrease in EUV light reflectance due to oxidation from 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. Is intended to reduce the reflectivity by forming a diffusion layer, and it is unclear whether the EUV light reflectivity is reduced by oxidation from the Ru protective layer as described above.
  • the present invention provides a substrate with a reflective layer for EUV lithography, a reflective mask blank for EUV lithography, and a reflective mask for EUV lithography in which a decrease in EUV light reflectance due to oxidation from a Ru protective layer is suppressed. And a method for manufacturing the substrate with a reflective layer for lithography.
  • 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 substrate with a reflective layer 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 substrate with a reflective layer (hereinafter also referred to as “the substrate with a reflective layer of the present invention” in the present specification) is provided.
  • the uppermost layer of the reflective layer made of the Mo / Si multilayer reflective film is a Si film, and the intermediate layer is provided on the Si film surface.
  • 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 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.
  • 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 present invention also provides an EUV lithography (hereinafter referred to as “UVV 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.
  • UVV lithography an EUV lithography
  • a method for producing a substrate with a reflective layer for EUVL comprising: 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 substrate with a reflective layer for EUVL wherein the protective layer is formed after forming the protective layer.
  • the temperature of the nitrogen-containing atmosphere is preferably 0 to 160 ° C.
  • the temperature of the nitrogen-containing atmosphere is 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, Is preferably irradiated with ultraviolet rays in order to promote nitrogen content on the Si layer surface.
  • the EUV mask produced using the EUV mask blank of the present invention is a highly reliable EUV mask in which the EUV light reflectivity is small with time during EUV exposure.
  • 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 an embodiment in which the absorber layer 15 and the low reflective layer 16 of the EUV mask blank 1 ′ of FIG.
  • 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 14 for protecting 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.
  • An absorber layer 15 is formed on the protective layer 14.
  • the substrate 11 satisfies 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 ⁇ 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.
  • the substrate 11 preferably has a smooth surface with a surface roughness rms of 0.15 nm or less and a flatness of 100 nm or less in order to obtain high reflectance and transfer accuracy in a photomask after pattern formation. .
  • 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. 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. However, even if it exists, 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 particularly required for the reflective layer 12 of the EUV mask blank 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)
  • Ar gas gas pressure 1.3 ⁇ 10 ⁇ 2 Pa to 2.7 ⁇ 10 ⁇ as a sputtering gas. 2 Pa
  • an Mo layer is deposited on the substrate surface so that the ion acceleration voltage is 300 to 1500 V, the deposition rate is 0.03 to 0.30 nm / sec, and the thickness is 2.3 nm.
  • the Si layer is formed by laminating the Mo layer and the Si layer for 40 to 50 periods.
  • the Mo layer constituting the Mo / Si multilayer reflective film and a part of the elements constituting the Si layer diffuse to adjacent layers, causing a decrease in reflectivity, that is, a decrease in reflectivity due to interdiffusion There is a case.
  • the cause of the decrease in reflectance is that oxidation from the top of the EUV mask blank is promoted by diffusion of Si from the uppermost Si layer of the multilayer reflective film to the protective layer.
  • the main reason is that due to oxidation from the upper layer of the Mo / Si multilayer reflective film.
  • 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 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. .
  • 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 nitrogen contained in the uppermost Si layer 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.
  • a process performed at the time of manufacturing a mask blank or a process performed when manufacturing a photomask from the mask blank for example, cleaning, defect inspection, heating process, dry etching, defect correction processes
  • the presence of the intermediate layer 13 having an effect of suppressing the oxidation causes the Mo / Si multilayer under the intermediate layer 13 to exist.
  • 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 either during the formation of the Si layer, which is the uppermost layer of the Mo / Si multilayer reflective film, or during the formation of the protective layer 14 formed on the intermediate layer 13, or It is considered that nitrogen was added at the time of film formation of both of them, but nitrogen was added when the intermediate layer was formed under the condition that the nitrogen content in the intermediate layer 13 exceeded 25 at%. Film formation causes problems due to an increase in defects during film formation.
  • the intermediate layer 13 contains 0.5 to 15 at% nitrogen, preferably contains 85 to 99.5 at% Si, contains 0.5 to 10 at% nitrogen, and contains 80 to 99.5 at% Si.
  • it contains 1 to 9 at% nitrogen, more preferably 91 to 99 at% Si, more preferably 3 to 9 at% nitrogen, and more preferably 91 to 97 at% Si. It is particularly preferable to contain 5 to 8 at% of Si and 92 to 95 at% of Si.
  • the intermediate layer 13 preferably does not contain fluorine. Further, if carbon or hydrogen is contained in the intermediate layer 13, it reacts with oxygen in the intermediate layer 13, and oxygen in the intermediate layer 13 is released, so that the structure of the intermediate layer 13 may be deteriorated. Therefore, it is preferable that the intermediate layer 13 does not contain carbon or hydrogen.
  • the content of fluorine, carbon and hydrogen in the intermediate layer 13 is preferably 3 at% or less, and more preferably 1 at% or less.
  • the content of elements such as Ni, Y, Ti, La, Cr or Rh in the intermediate layer 13 prevents the surface roughness from increasing due to the difference in etching rate when the mask blank is etched. The total content of these elements is preferably 3 at% or less, and more preferably 1 at% or less.
  • 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 a predetermined amount of nitrogen and Si may not 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 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 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., 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 surface of the Si layer which is the uppermost layer of the Mo / Si multilayer reflective film, is exposed to a nitrogen-containing atmosphere to lightly nitride the Si layer surface, that is, the Si layer surface contains nitrogen. Therefore, it is preferable to form the intermediate film 13 because the EUV light reflectance after the formation of the protective layer 14 (Ru protective layer) does not decrease 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, was 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 Si layer surface is heat-treated in a nitrogen-containing atmosphere is preferably 120 to 160 ° C., particularly 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 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 protective layer 14 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 15 is patterned by an etching process, usually a dry etching process. Therefore, as the material of the protective layer 14, a material that is not easily affected by the etching process of the absorber layer 15, that is, the etching rate is slower than that of the absorber layer 15 and is not easily damaged by the etching process is selected.
  • 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 or a Ru compound layer is formed as the protective layer 14 in order to satisfy the above conditions.
  • the Ru compound of the Ru compound layer at least one selected from the group consisting of RuB, RuNb, and RuZr is preferable.
  • the Ru content is preferably 50 at% or more, 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%, particularly 5 to 30 at%.
  • Si may diffuse slightly from the adjacent intermediate layer 13.
  • the Si content in the protective layer 14 is preferably 0.1 to 4.5 at%, and preferably 0.1 to 4 at%. More preferred.
  • the composition may be such that the Si content in the protective layer 14 is inclined so that the Si content is high and the Si content near the interface with the absorber layer 15 is low.
  • the Si content near the interface with the absorber layer 15 is preferably low, and specifically, it is preferably 4 at% or less, and Si near the interface with the absorber layer 15 is Si. It is more preferable not to contain.
  • Nitrogen may also diffuse into the protective layer 14 slightly from the adjacent intermediate layer 13.
  • the nitrogen content in the protective layer 14 is preferably 0.1 to 10 at%, and more preferably 0.1 to 5 at%.
  • the composition may be such that the nitrogen content in the protective layer 14 is inclined such that the nitrogen content in the protective layer 14 is high and the nitrogen content in the vicinity of the interface with the absorber layer 15 is low.
  • the characteristics of the protective layer 14 are hardly deteriorated.
  • the surface roughness rms on the surface of the protective layer 14 is preferably 0.5 nm or less.
  • the surface roughness of the surface of the protective layer 14 is large, the surface roughness of the absorber layer 15 formed on the protective layer 14 increases, and the edge roughness of the pattern formed on the absorber layer 15 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 15 is required to be smooth. If the surface roughness rms of the surface of the protective layer 14 is 0.5 nm or less, the surface of the absorber layer 15 formed on the protective layer 14 is sufficiently smooth, so that 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 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 and the etching resistance can be obtained.
  • 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.
  • Film formation rate 0.03 to 0.30 nm / sec.
  • the state before forming the absorber layer of the EUV mask blank of the present invention that is, the structure excluding the absorber layer 15 of the mask blank 1 shown in FIG. 1 is the substrate with a reflective layer of the present invention.
  • the substrate with a reflective layer of the present invention is a precursor of an EUV mask blank.
  • the decrease in EUV light reflectance before and after cleaning is 0.9% or less. It is preferably 0.5% or less.
  • the decrease in EUV light reflectance before and after the heat-treatment is 7% or less, 6%
  • 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
  • the characteristic particularly required for the absorber layer 15 is that the EUV light reflectance is extremely low. Specifically, when the surface of the absorber layer 15 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).
  • Such an absorber layer 15 is preferably a film containing Ta as a main component, and particularly a film containing TaN or TaBN as a main component.
  • TaBSiN film examples 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%.
  • Ta content preferably 50 to 90 at%, more preferably 60 to 80 at%.
  • N content preferably 5 to 30 at%, more preferably 10 to 25 at%.
  • the absorber layer 15 having the above composition has an amorphous crystal state and excellent surface smoothness.
  • the absorber layer 15 having the above composition preferably has a surface roughness rms of 0.5 nm or less. If the surface roughness of the surface of the absorber layer 15 is large, the edge roughness of the pattern formed on the absorber layer 15 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 15 is required to be smooth.
  • the surface roughness rms of the surface of the absorber layer 15 is 0.5 nm or less, the surface of the absorber 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 on the surface of the absorber layer 15 is more preferably 0.4 nm or less, and further preferably 0.3 nm or less.
  • the etching rate is high when dry etching is performed using a chlorine-based gas as an etching gas, and the etching selectivity with the protective layer 14 is 10 or more.
  • the etching selectivity can be calculated using the following equation (1).
  • Etching selectivity (etching rate of absorber layer 15) / (etching rate of protective layer 14) (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 15 is preferably 50 to 100 nm.
  • the absorption layer 15 having the above-described configuration can be formed by 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 16 for inspection light used for inspection of a mask pattern is preferably formed on the absorber layer 15 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 15 is removed by pattern formation and the surface of the absorber layer 15 remaining without being removed by pattern formation, It is inspected by the difference in reflectance.
  • the former is the surface of the protective layer 14. Therefore, if the difference in reflectance between the surface of the protective layer 14 and the surface of the absorber layer 15 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 15 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 on the surface of the absorber layer 15 and the reflectance on the surface of the protective layer 14 at the wavelength of the inspection light becomes small, and there is a possibility that sufficient contrast at the time of 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 16 is formed on the absorber layer 15 to improve the contrast at the time of inspection. In other words, at the wavelength of the inspection light.
  • the light reflectance is extremely low.
  • the low reflection layer 16 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 the 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 16 is 15% or less, the contrast during 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 14 and the reflected light having the wavelength of the inspection light on the surface of the low reflection layer 16 is 30% or more, preferably 40% or more.
  • Contrast (%) ((R 2 ⁇ R 1 ) / (R 2 + R 1 )) ⁇ 100 (2)
  • R 2 at the wavelength of the inspection light is a reflectance at the surface of the protective layer 14
  • R 1 is a reflectance at the surface of the low reflective layer 16. Note that R 1 and R 2 are measured in a state where patterns are formed on the absorber layer 15 and the low reflection layer 16 of the EUV mask blank 1 ′ shown in FIG. 2 (that is, the state shown in FIG. 3).
  • FIG. 3 the state shown in FIG.
  • R 2 is a value measured on the surface of the protective layer 14 exposed to the outside after the absorber layer 15 and the low reflection layer 16 are removed by pattern formation, and R 1 is not removed by pattern formation. This is a value measured on the surface of the remaining low reflection layer 16.
  • the contrast represented by the above formula is more preferably 45% or more, further preferably 60% or more, and particularly preferably 80% or more.
  • the low reflection layer 16 is preferably made of a material whose refractive index at the wavelength of the inspection light is lower than that of the absorber layer 15, and its crystal state is preferably amorphous.
  • a specific example of such a low reflection layer 16 is preferably a film mainly composed of Ta and oxygen, and particularly a film mainly composed of TaNO or TaBNO.
  • Other examples 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%.
  • the low reflection layer 16 include those containing Ta, B, Si, O, and N in the ratios described below (low reflection 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 reflection layer (TaBSiO), (TaBSiON)
  • its crystal state is amorphous and its surface is excellent in smoothness.
  • the surface roughness rms of the surface of the low reflection layer ((TaBSiO), (TaBSiON)) is preferably 0.5 nm or less.
  • the surface of the absorber layer 15 is required to be smooth in order to prevent deterioration of the dimensional accuracy of the pattern due to the influence of edge roughness. Since the low reflection layer 16 is formed on the absorber layer 15, the surface thereof is required to be smooth for the same reason.
  • the surface roughness rms of the surface of the low reflective layer 16 is 0.5 nm or less, the surface of the low reflective layer 16 is sufficiently smooth, and the dimensional accuracy of the pattern does not deteriorate due to the influence of edge roughness.
  • the surface roughness rms of the surface of the low reflective layer 16 is more preferably 0.4 nm or less, and further preferably 0.3 nm or less.
  • the total thickness of the absorber layer 15 and the low reflective layer 16 is preferably 55 to 130 nm. Further, if the thickness of the low reflection layer 16 is larger than the thickness of the absorber layer 15, the EUV light absorption characteristics in the absorber layer 15 may be deteriorated. Therefore, the thickness of the low reflection layer 16 is determined by the absorber layer. It is preferred that the thickness is less than 15. Therefore, the thickness of the low reflection layer 16 is preferably 5 to 30 nm, and more preferably 10 to 20 nm.
  • the low reflection layer (TaBSiO), (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 16 is preferably formed on the absorber layer 15 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 (near 13.5 nm) is used as pattern inspection light, it is considered unnecessary to form the low reflection layer 16 on the absorber layer 15.
  • 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 16 on the absorber layer 15.
  • 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, as described in JP-A-2003-501823 (incorporated as the disclosure of the present application specification), in order to promote electrostatic chucking of the substrate, 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 forming 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
  • a CVD method a vacuum evaporation method
  • electrolytic plating method electrolytic plating method
  • the present invention also provides an EUV mask patterned on the EUV mask blank.
  • the EUV mask of the present invention is produced by patterning at least the absorber layer of the EUV mask blank of the present invention (in the case where a low reflection layer is formed on the absorber layer), the absorber layer and the low reflection layer). be able to.
  • 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 is 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 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 layer and then the Si layer using the beam sputtering method.
  • a reflective layer 12) was formed.
  • the uppermost layer of the multilayer reflective film 12 is a Si layer.
  • the film forming conditions for the Mo layer and the Si layer are as follows.
  • Mo layer deposition 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 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. Film forming speed: 0.052 nm / sec. -Film thickness: 2.5 nm.
  • TaBSiN layer is formed as the absorber layer 15 on the protective layer 14 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 decrease in EUV reflectance before and after this treatment was 0.5%.
  • Heat treatment resistance The sample formed up to the protective layer 14 by the above procedure was subjected to heat treatment (atmosphere) at 210 ° C. for 10 minutes. The decrease in EUV reflectance before and after this treatment was 4.1%.
  • Reflection characteristics About the sample formed to the protective layer 14 in said procedure, the reflectance of the pattern test
  • the reflectance on the surface of the protective layer 14 is 60.0%, and the reflectance on the surface of the low reflective layer 16 is 6.9%.
  • the contrast is 79.4%.
  • the EUV light (wavelength 13.5nm) is irradiated to the surface of the low reflection layer 16, and the reflectance of EUV light is measured.
  • the reflectance of EUV light is 0.4%, and it is confirmed that the EUV absorption characteristics are excellent.
  • Etching characteristics The etching characteristics are evaluated by the following method instead of using the EUV mask blank produced by the above procedure.
  • a Si chip (10 mm ⁇ 30 mm) on which a Ru film or a TaBSiN film is formed by a method described below is installed as a sample.
  • the Ru film or TaNBSiN film of the Si chip placed on the sample stage is subjected to plasma RF etching under the following conditions.
  • -Bias RF 50W.
  • Etching time 120 sec.
  • -Trigger pressure 3Pa.
  • Etching pressure 1 Pa.
  • Etching gas Cl 2 / Ar.
  • the Ru film is formed by ion beam sputtering under the following film formation conditions.
  • Target Ru target.
  • Sputtering gas Ar gas (gas pressure: 2 mTorr, flow rate: 15 sccm).
  • -Output 150W.
  • Film forming speed 0.023 nm / sec.
  • Film thickness 2.5nm
  • TaBSiN film formation conditions (1) Target: TaB target (composition ratio: Ta 80 at%, B 20 at%), Si target.
  • Sputtering gas Ar and N 2 mixed gas (Ar: 86% by volume, N 2 : 14% by volume, gas pressure: 2 mTorr (0.3 Pa)). Output: 150 W (TaB target), 30 W (Si target). Film forming speed: 0.13 nm / sec. -Film thickness: 60 nm. (TaBSiN film formation conditions (2)) Target: TaB target (composition ratio: Ta 80 at%, B 20 at%), Si target.
  • Sputtering gas Ar gas, N 2 gas (Ar: 86% by volume, N 2 : 14% by volume, gas pressure: 2 mTorr (0.3 Pa)). Output: 150 W (TaB target), 50 W (Si target).
  • Film forming speed 0.12 nm / sec. -Film thickness: 60 nm.
  • Target TaB target (composition ratio: Ta 80 at%, B 20 at%), Si target.
  • Sputtering gas Ar gas, N 2 gas (Ar: 86 vol%, N 2 : 14 vol%, gas pressure: 2 mTorr (0.3 Pa), flow rate: 13 sccm (Ar), 2 sccm (N 2 )).
  • Output 150 W (TaB target), 100 W (Si target).
  • Film forming speed 0.11 nm / sec. -Film thickness: 60 nm.
  • the etching rate is obtained for the Ru film and the TaBSiN films (1) to (3) formed under the above conditions, and the etching selectivity is obtained using the following equation (3).
  • Etching selectivity (etching rate of TaBSiN film) / (etching rate of Ru film) (3)
  • the etching selectivity with the protective layer 13 is preferably 10 or more, but the TaBSiN films (1) to (3)
  • the etching selectivity is as follows, and all have sufficient selectivity.
  • Example 2 Example 2 was carried out in the same procedure as Example 1 except that the conditions for exposure to the nitrogen-containing atmosphere were as follows. (Exposure conditions) Carrier gas: Ar gas, flow rate 17 sccm. Exposed gas: Nitrogen gas, flow rate 50 sccm. (Nitrogen gas and carrier gas are supplied during RF discharge). Nitrogen gas partial pressure: 0.2 mTorr (2.6 ⁇ 10 ⁇ 2 Pa). Atmospheric pressure: 0.3 mTorr (3.5 ⁇ 10 ⁇ 2 Pa) -Atmospheric temperature: 20 degreeC. -Exposure time: 6000 sec.
  • -Frequency of RF discharge 1.8 MHz.
  • -RF power 500W.
  • the film thickness of the intermediate layer 13 was 1 nm.
  • the surface roughness of the protective layer 14 is measured according to JIS-B0601 (1994) by an atomic force microscope (Seiko Instruments). It confirmed using the company make: number SPI3800). The surface roughness rms of the protective layer 14 was 0.15 nm.
  • Washing resistance With respect to the sample formed up to the protective layer 14 by the above procedure, the surface of the protective layer 14 was treated for 600 seconds by spin cleaning with ozone water.
  • 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%.
  • (4) Heat treatment resistance The sample formed up to the protective layer 14 by the above procedure is subjected to a heat treatment (in air) at 210 ° C. for 10 minutes. The decrease in EUV reflectivity before and after this treatment is 3.7%.
  • Example 3 In place of exposure to the nitrogen-containing atmosphere (nitrogen and argon mixed gas atmosphere) on the surface of the Si layer where RF discharge is performed, heat treatment was performed under the following exposure conditions where RF discharge was not performed. The same procedure as in Example 1 was performed. 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. Nitrogen gas, flow rate 50 sccm.
  • the surface roughness of the protective layer 14 is measured according to JIS-B0601 (1994) by an atomic force microscope (Seiko Instruments). Confirm using a product number: SPI3800). The surface roughness rms of the protective layer 14 is 0.15 nm.
  • Washing resistance With respect to the sample formed up to the protective layer 14 by the above procedure, the surface of the protective layer 14 is treated for 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 sample formed up to the protective layer 14 by the above procedure is subjected to a heat treatment (in air) at 210 ° C. for 10 minutes. The decrease in EUV reflectivity before and after this treatment is 4.3%.
  • Example 4 performs the same procedure as Example 3 except that the exposure conditions in a nitrogen-containing atmosphere (in a mixed gas atmosphere of nitrogen and argon) are as follows. (Exposure conditions) Atmospheric gas: Ar gas (carrier gas), flow rate 17 sccm. Nitrogen gas, flow rate 50 sccm. 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: 140 ° C. -Heat treatment time: 6000 sec.
  • the surface roughness of the protective layer 14 is measured according to JIS-B0601 (1994) by an atomic force microscope (Seiko Instruments). Confirm using a product number: SPI3800). The surface roughness rms of the protective layer 14 is 0.15 nm.
  • Washing resistance With respect to the sample formed up to the protective layer 14 by the above procedure, the surface of the protective layer 14 is treated for 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 sample formed up to the protective layer 14 by the above procedure is subjected to a heat treatment (in air) at 210 ° C. for 10 minutes. 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.
  • 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 17 sccm (Ar gas is supplied during RF discharge). Atmospheric pressure: 0.1 mTorr (1.3 ⁇ 10 ⁇ 2 Pa) -Atmospheric temperature: 20 degreeC. ⁇ Exposure time: 600 sec. -Frequency of RF discharge: 1.8 MHz. -RF power: 500W.
  • 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).
  • a nitrogen-containing atmosphere a mixed gas atmosphere of nitrogen and argon
  • the surface roughness of the protective layer 14 is measured according to JIS-B0601 (1994) by an atomic force microscope (Seiko Instruments). Confirm using a product number: SPI3800). The surface roughness rms of the protective layer 14 is 0.15 nm.
  • Washing resistance With respect to the sample formed up to the protective layer 14 by the above procedure, the surface of the protective layer 14 is treated for 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).
  • 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 17 sccm.
  • Atmospheric pressure 0.1 mTorr (1.3 ⁇ 10 ⁇ 2 Pa)
  • -Heat treatment temperature 140 ° C.
  • -Heat treatment time 600 sec.
  • the surface roughness of the protective layer 14 is measured according to JIS-B0601 (1994) by an atomic force microscope (Seiko Instruments). Confirm using a product number: SPI3800). The surface roughness rms of the protective layer 14 is 0.15 nm.
  • Washing resistance With respect to the sample formed up to the protective layer 14 by the above procedure, the surface of the protective layer 14 is treated for 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%. From this result, it is confirmed that the mask blank of Comparative Example 4 is inferior in cleaning resistance as compared with the mask blanks of Examples 1 to 4.
  • Heat treatment resistance The sample formed up to the protective layer 14 by the above procedure is subjected to a heat treatment (in air) at 210 ° C. for 10 minutes. The decrease in EUV reflectance before and after this treatment is 7.8%. From this result, it is confirmed that the mask blank of Comparative Example 4 is inferior in heat treatment resistance compared to the mask blanks of Examples 1 to 4.
  • 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).
  • Exposed gas Atmosphere (N 2 : about 78% by volume, O 2 : about 21% by volume).
  • Atmospheric pressure 760 Torr (1.0 ⁇ 10 5 Pa).
  • -Atmospheric temperature 20 degreeC.
  • Exposure time 600 sec.
  • Atmospheric gas Ar gas (carrier gas), flow rate 17 sccm. Nitrogen gas, flow rate 50 sccm.
  • the following evaluation is performed on the mask blank obtained by the above procedure.
  • Film composition For the sample formed up to the protective layer 14 by the above procedure, the composition in the depth direction from the surface of the protective layer 14 to the reflective layer (Mo / Si multilayer reflective film) 12 was measured using an X-ray photoelectron spectrometer (X -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 by measuring using ray Photoelectron Spectrometer (manufactured by ULVAC-PHI, Inc .: Quantera SXM). Make sure.
  • the composition of the intermediate layer 13 is oxygen 4 at%, nitrogen 1 at%, and Si 95 at%.
  • the film thickness of the intermediate layer 13 is 1 nm.
  • the surface roughness of the protective layer 14 is measured according to JIS-B0601 (1994) by an atomic force microscope (Seiko Instruments). Confirm using a product number: SPI3800). The surface roughness rms of the protective layer 14 is 0.15 nm.
  • Washing resistance With respect to the sample formed up to the protective layer 14 by the above procedure, the surface of the protective layer 14 is treated for 600 seconds by spin cleaning with ozone water.
  • 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).
  • MRR product name
  • the decrease in EUV reflectivity before and after this treatment is 0.8%. From this result, it is confirmed that the mask blank of Comparative Example 5 has improved cleaning resistance as compared with Comparative Example 1, but is inferior to the mask blank of Examples 1 to 4 in cleaning resistance.
  • (4) Heat treatment resistance The sample formed up to the protective layer 14 by the above procedure is subjected to a heat treatment (in air) at 210 ° C. for 10 minutes. The decrease in EUV reflectance before and after this treatment is 8.1%. From this result, it is confirmed that the mask blank of Comparative Example 5 is inferior in heat treatment resistance compared to the mask blanks of Examples 1 to 4.
  • Example 5 In 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. (Exposure conditions) Carrier gas: Ar gas, flow rate 17 sccm. Exposed gas: Nitrogen gas, flow rate 50 sccm. Nitrogen gas partial pressure: 0.2 mTorr (2.6 ⁇ 10 ⁇ 2 Pa). Atmospheric pressure: 0.3 mTorr (3.5 ⁇ 10 ⁇ 2 Pa) -Atmospheric temperature: 20 degreeC.
  • Carrier gas Ar gas, flow rate 17 sccm.
  • Exposed gas Nitrogen gas, flow rate 50 sccm.
  • Nitrogen gas partial pressure 0.2 mTorr (2.6 ⁇ 10 ⁇ 2 Pa).
  • UV light source Argon excimer lamp. UV wavelength: 126 nm.
  • the film thickness of the intermediate layer 13 was 1 nm.
  • the surface roughness of the protective layer 14 is measured according to JIS-B0601 (1994) by an atomic force microscope (Seiko Instruments). It confirmed using the company make: number SPI3800). The surface roughness rms of the protective layer 14 was 0.15 nm.
  • Washing resistance With respect to the sample formed up to the protective layer 14 by the above procedure, the surface of the protective layer 14 was treated for 600 seconds by spin cleaning with ozone water.
  • 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%.
  • (4) Heat treatment resistance The sample formed up to the protective layer 14 by the above procedure is subjected to a heat treatment (in air) at 210 ° C. for 10 minutes. The decrease in EUV reflectivity before and after this treatment is 3.7%.
  • 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 a more miniaturized semiconductor. Useful in the manufacture of integrated circuits.

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Abstract

La présente invention a trait à une ébauche de masque d'ultraviolets extrêmes permettant d'empêcher toute réduction du pouvoir réfléchissant causée par l'oxydation se produisant à partir de la couche de protection Ru, à un substrat équipé d'une couche réfléchissante utilisé pour produire l'ébauche de masque d'ultraviolets extrêmes, et à un processus de production du substrat équipé d'une couche réfléchissante. Le substrat équipé d'une couche réfléchissante selon la présente invention pour lithographie par ultraviolets extrêmes est doté 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, et 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 0,5 % à 25 % par atome d'azote et 75 % à 99,5 % par atome de Si est formée entre la couche réfléchissante et la couche de protection.
PCT/JP2010/072161 2009-12-09 2010-12-09 Substrat équipé d'une couche réfléchissante pour lithographie par ultraviolets extrêmes, ébauche de masque réfléchissant pour lithographie par ultraviolets extrêmes, masque réfléchissant pour lithographie par ultraviolets extrêmes et processus de production de substrat équipé d'une couche réfléchissante Ceased WO2011071123A1 (fr)

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KR1020127012513A KR101699574B1 (ko) 2009-12-09 2010-12-09 Ｅｕｖ 리소그래피용 반사층이 형성된 기판, ｅｕｖ 리소그래피용 반사형 마스크 블랭크, ｅｕｖ 리소그래피용 반사형 마스크, 및 그 반사층이 형성된 기판의 제조 방법
CN2010800562668A CN102687071B (zh) 2009-12-09 2010-12-09 带反射层的euv光刻用衬底、euv光刻用反射型掩模坯料、euv光刻用反射型掩模、和该带反射层的衬底的制造方法
EP10836043.9A EP2511944A4 (fr) 2009-12-09 2010-12-09 Substrat équipé d'une couche réfléchissante pour lithographie par ultraviolets extrêmes, ébauche de masque réfléchissant pour lithographie par ultraviolets extrêmes, masque réfléchissant pour lithographie par ultraviolets extrêmes et processus de production de substrat équipé d'une couche réfléchissante
JP2011545247A JP5673555B2 (ja) 2009-12-09 2010-12-09 Ｅｕｖリソグラフィ用反射層付基板、ｅｕｖリソグラフィ用反射型マスクブランク、ｅｕｖリソグラフィ用反射型マスク、および該反射層付基板の製造方法
US13/478,532 US8993201B2 (en) 2009-12-09 2012-05-23 Reflective layer-equipped substrate for EUV lithography, reflective mask blank for EUV lithography, reflective mask for EUV lithography, and process for production of the reflective layer-equipped substrate

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JP2014229825A (ja) * 2013-05-24 2014-12-08 旭硝子株式会社 Ｅｕｖリソグラフィ用反射型マスクブランクの製造方法および、該マスクブランク用の反射層付基板の製造方法
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US20120231378A1 (en) 2012-09-13
US8580465B2 (en) 2013-11-12
JPWO2011071123A1 (ja) 2013-04-22
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