WO2015098400A1 - 反射型マスクブランク及び反射型マスク、並びに半導体装置の製造方法 - Google Patents
反射型マスクブランク及び反射型マスク、並びに半導体装置の製造方法 Download PDFInfo
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- WO2015098400A1 WO2015098400A1 PCT/JP2014/081153 JP2014081153W WO2015098400A1 WO 2015098400 A1 WO2015098400 A1 WO 2015098400A1 JP 2014081153 W JP2014081153 W JP 2014081153W WO 2015098400 A1 WO2015098400 A1 WO 2015098400A1
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- film
- reflective mask
- phase shift
- layer
- mask blank
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- 229910001936 tantalum oxide Inorganic materials 0.000 description 5
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Images
Classifications
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
- G03F1/22—Masks or mask blanks for imaging by radiation of 100nm or shorter wavelength, e.g. X-ray masks, extreme ultraviolet [EUV] masks; Preparation thereof
- G03F1/24—Reflection masks; Preparation thereof
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0641—Nitrides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/18—Metallic material, boron or silicon on other inorganic substrates
- C23C14/185—Metallic material, boron or silicon on other inorganic substrates by cathodic sputtering
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
- G03F1/26—Phase shift masks [PSM]; PSM blanks; Preparation thereof
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
- G03F1/38—Masks having auxiliary features, e.g. special coatings or marks for alignment or testing; Preparation thereof
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
- G03F1/38—Masks having auxiliary features, e.g. special coatings or marks for alignment or testing; Preparation thereof
- G03F1/48—Protective coatings
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- 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
- G03F7/20—Exposure; Apparatus therefor
- G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
- G03F7/2004—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image characterised by the use of a particular light source, e.g. fluorescent lamps or deep UV light
Definitions
- the present invention relates to a reflective mask blank which is an original for manufacturing an exposure mask used for manufacturing a semiconductor device and the like, a reflective mask manufactured thereby, and a method for manufacturing a semiconductor device.
- EUV lithography using an extreme ultra violet (EUV) having a wavelength of around 13.5 nm has been proposed.
- EUV lithography a reflective mask is used because the difference in absorption rate between materials for EUV light is small.
- a multilayer reflective film that reflects exposure light is formed on a substrate, and a phase shift film that absorbs exposure light is formed in a pattern on a protective film for protecting the multilayer reflective film.
- the light incident on the reflective mask mounted on the exposure machine is absorbed by the part with the phase shift film pattern and reflected by the multilayer reflective film at the part without the phase shift film pattern.
- An image is transferred onto a semiconductor substrate through a reflective optical system. Part of the exposure light incident on the phase shift film pattern is reflected with a phase difference of about 180 degrees from the light reflected by the multilayer reflective film (phase shift), thereby obtaining a contrast.
- Patent Documents 1 to 4 disclose technologies related to such a reflective mask for EUV lithography and a mask blank for producing the same.
- the EUV exposure machine is a technology that has not yet reached full-scale commercialization, and the power of the exposure light source that is suitable for research and development is selected (a light source of about 15 W is currently used) It is.
- the power of the exposure light source that is suitable for research and development is selected (a light source of about 15 W is currently used) It is.
- full-scale commercialization it is naturally necessary to obtain a certain throughput or higher.
- the exposure light source becomes high power, the amount of heat generated per unit time in the reflective mask during exposure (pattern transfer) also increases (because the energy of light absorbed by the phase shift film is converted into heat). Due to thermal diffusion due to heat, mutual diffusion occurs between the protective film and the material of the phase shift film pattern adjacent thereto. Due to such interdiffusion, the reflectance with respect to the EUV light varies, and the function as a reflective mask may be degraded by repeated use (the contrast as designed cannot be obtained).
- the present invention provides an EUV by means of mutual diffusion due to thermal diffusion between the protective film and the material of the phase shift film pattern adjacent to the protective film even when the exposure light source of the EUV exposure machine is increased in power. It is an object of the present invention to provide a reflective mask blank that can prevent the reflectivity of light from fluctuating, a reflective mask manufactured thereby, and a method for manufacturing a semiconductor device.
- the present invention has the following configuration.
- a reflective mask blank in which a multilayer reflective film, a protective film, and a phase shift film for shifting the phase of EUV light are formed in this order on a substrate, and the protective film is made of a material containing ruthenium as a main component.
- the phase shift film has a tantalum-based material layer containing tantalum, and is formed on the surface of the protective film or on the side in contact with the phase shift layer as a part of the protective film.
- a reflective mask blank wherein a diffusion prevention layer containing ruthenium and oxygen for suppressing diffusion is formed.
- phase shift film is formed by a sputtering method, and has a laminated structure in which films are continuously formed without being exposed to the atmosphere from the start of film formation to the end of film formation. Reflective mask blank.
- the uppermost layer of the multilayer reflective film is silicon (Si), and has a silicon oxide layer containing silicon and oxygen between the uppermost layer and the protective film.
- a semiconductor device comprising a step of setting a reflective mask according to Configuration 10 in an exposure apparatus having an exposure light source that emits EUV light, and transferring a transfer pattern to a resist film formed on a transfer substrate. Manufacturing method.
- the reflective mask blank of the present invention (the reflective mask produced thereby), a diffusion prevention layer containing ruthenium and oxygen on the surface of the protective film or on the side in contact with the phase shift layer as a part of the protective film
- a diffusion prevention layer containing ruthenium and oxygen on the surface of the protective film or on the side in contact with the phase shift layer as a part of the protective film
- the mutual diffusion due to thermal diffusion between the protective film and the phase shift film (absorber film) is suppressed even under the use environment where the exposure light source of the EUV exposure machine is high power, and the reflectance of the EUV light is reduced. Is suppressed. Therefore, a reflective mask that suppresses a decrease in the phase shift effect can be obtained.
- the method for manufacturing a semiconductor device of the present invention it is possible to provide a method for manufacturing a semiconductor device that similarly suppresses a decrease in the phase shift effect in the reflective mask.
- FIG. 1 The schematic diagram which shows the process of producing the reflective mask for EUV lithography from the reflective mask blank for EUV lithography of Example 1.
- FIG. 2 The schematic diagram which shows the process of producing the reflective mask for EUV lithography from the reflective mask blank for EUV lithography of Example 2.
- FIG. 3 The schematic diagram which shows the process of producing the reflective mask for EUV lithography from the reflective mask blank for EUV lithography of Example 3.
- FIG. 1 The schematic diagram which shows the process of producing the reflective mask for EUV lithography from the reflective mask blank for EUV lithography of Example 1.
- FIG. 1 is a schematic view for explaining the configuration of a reflective mask blank for EUV lithography according to the present invention.
- the reflective mask blank 10 is mainly composed of a substrate 12, a multilayer reflective film 13 that reflects EUV light as exposure light, and ruthenium for protecting the multilayer reflective film 13.
- the diffusion prevention layer 15 made of a material containing ruthenium and oxygen, and to absorb EUV light, reflect some EUV light, and shift its phase.
- the phase shift films 16 are stacked in this order.
- a back surface conductive film 11 for electrostatic chuck is formed on the back surface side of the substrate 12.
- a substrate having a low thermal expansion coefficient within a range of 0 ⁇ 5 ppb / ° C. is preferably used for the substrate 12 to prevent distortion of the absorber film pattern due to heat during exposure with EUV light.
- a material having a low thermal expansion coefficient in this range for example, SiO 2 —TiO 2 glass, multicomponent glass ceramics, and the like can be used.
- the main surface of the substrate 12 on which a transfer pattern (a phase shift film described later constitutes this) is formed is surface-processed to have high flatness from the viewpoint of obtaining at least pattern transfer accuracy and position accuracy.
- the flatness is preferably 0.1 ⁇ m or less, more preferably 0.05 ⁇ m or less, particularly preferably in a 132 mm ⁇ 132 mm region of the main surface on the side where the transfer pattern of the substrate 12 is formed. 0.03 ⁇ m or less.
- the main surface opposite to the side on which the phase shift film is formed is a surface that is electrostatically chucked when being set in the exposure apparatus, and its flatness is 1 ⁇ m or less in the 142 mm ⁇ 142 mm region.
- the flatness is a value representing the warpage (deformation amount) of the surface indicated by TIR (Total Indicated Reading), and a plane defined by the least square method with respect to the substrate surface is defined as a focal plane. It is the absolute value of the height difference between the highest position on the substrate surface above the plane and the lowest position on the substrate surface below the focal plane.
- the surface smoothness required for the substrate 12 is that the surface roughness of the main surface on the side where the transfer pattern of the substrate 12 is formed is 0.1 nm or less in terms of root mean square roughness (RMS). It is preferable that The surface smoothness can be measured with an atomic force microscope.
- the substrate 12 has high rigidity in order to prevent deformation due to film stress of a film (such as the multilayer reflective film 13) formed thereon.
- a film such as the multilayer reflective film 13
- those having a high Young's modulus of 65 GPa or more are preferable.
- the multilayer reflective film 13 provides a function of reflecting EUV light in a reflective mask for EUV lithography, and has a multilayer film structure in which elements having different refractive indexes are periodically stacked.
- a thin film (high refractive index layer) of a light element or a compound thereof, which is a high refractive index material, and a thin film (low refractive index layer) of a heavy element or a compound thereof, which is a low refractive index material, are alternately 40
- a multilayer film having about 60 cycles is used as the multilayer reflective film 13.
- the multilayer film may be laminated in a plurality of periods, with a laminated structure of a high refractive index layer / low refractive index layer in which a high refractive index layer and a low refractive index layer are laminated in this order from the substrate 12 side.
- a low-refractive index layer and a high-refractive index layer in which the low-refractive index layer and the high-refractive index layer are stacked in this order may be stacked in a plurality of periods.
- the outermost layer of the multilayer reflective film 13, that is, the surface layer opposite to the substrate 12 of the multilayer reflective film 13, is preferably a high refractive index layer.
- the uppermost layer has a low refractive index.
- the low refractive index layer constitutes the outermost surface of the multilayer reflective film 13, it is easily oxidized and the reflectance of the reflective mask is reduced. It is preferable to form a multilayer reflective film 13 by further forming a high refractive index layer.
- the stack structure is one cycle. Since the upper layer is a high refractive index layer, it can be left as it is.
- a layer containing Si is employed as the high refractive index layer.
- the material containing Si may be Si compound containing B, C, N, and O in addition to Si alone.
- a reflective mask for EUV lithography having excellent EUV light reflectivity can be obtained.
- a glass substrate is preferably used as the substrate 12, Si is excellent in adhesion to it.
- a single metal selected from Mo, Ru, Rh, and Pt, or an alloy thereof is used for the low refractive index layer.
- a Mo / Si periodic laminated film in which Mo films and Si films are alternately laminated for about 40 to 60 cycles is preferably used.
- a silicon oxide containing silicon and oxygen is formed between the uppermost layer (Si) and the Ru-based protective film 14 by forming a high refractive index layer that is the uppermost layer of the multilayer reflective film 13 with silicon (Si).
- a layer may be formed.
- the reflectance of the multilayer reflective film 13 alone is usually 65% or more, and the upper limit is usually 73%.
- the thickness and period of each constituent layer of the multilayer reflective film 13 may be appropriately selected depending on the exposure wavelength, and are selected so as to satisfy Bragg's law.
- the multilayer reflective film 13 includes a plurality of high refractive index layers and low refractive index layers, but the thicknesses of the high refractive index layers and the low refractive index layers may not be the same.
- the film thickness of the outermost Si layer of the multilayer reflective film 13 can be adjusted within a range in which the reflectance is not lowered.
- the film thickness of the outermost Si (high refractive index layer) can be 3 to 10 nm.
- the method of forming the multilayer reflective film 13 is known in the art, but can be formed by depositing each layer by, for example, ion beam sputtering.
- an Si film having a thickness of about 4 nm is first formed on the substrate 12 using an Si target, for example, by ion beam sputtering, and then about 3 nm in thickness using a Mo target.
- the Mo film is formed, and this is set as one period, and is laminated for 40 to 60 periods to form the multilayer reflective film 13 (the outermost layer is a Si layer).
- the Ru-based protective film 14 is formed on the multilayer reflective film 13 in order to protect the multilayer reflective film 13 from dry etching and cleaning in the manufacturing process of the reflective mask for EUV lithography described later.
- the Ru-based protective film 14 is made of a material containing ruthenium as a main component (main component: 50 at% or more), and may be a Ru metal alone, or Nb, Zr, Y, B, Ti, La, Mo, Co, and Ru. Ru alloys containing metals such as Re and Ni may also be included.
- the Ru-based protective film 14 has a laminated structure of three or more layers, and the lowermost layer and the uppermost layer are layers made of a substance containing Ru, and a metal other than Ru, or between the lowermost layer and the uppermost layer, An alloy may be interposed.
- the thickness of the Ru-based protective film 14 composed of such Ru or an alloy thereof is not particularly limited as long as it can function as the protective film. From the viewpoint of EUV light reflectance, The thickness is 1.5 to 8.0 nm, more preferably 1.8 to 6.0 nm.
- a method for forming the Ru-based protective film 14 a method similar to a known film forming method can be employed without any particular limitation. Specific examples include a sputtering method and an ion beam sputtering method.
- a phase shift film 16 is formed on the Ru-based protective film 14 via a diffusion prevention layer 15 described later.
- the phase shift film 16 absorbs EUV light and reflects a part thereof to shift the phase. That is, in the reflective mask on which the phase shift film 16 is patterned, the part where the phase shift film 16 remains is partially reflected so that the pattern transfer is not affected while absorbing EUV light.
- the phase difference with the reflected light from 13 is formed.
- the phase shift film 16 is formed so that the reflectance with respect to EUV light is 1 to 30%, and the phase difference between the reflected light from the phase shift film 16 and the reflected light from the multilayer reflective film 13 is 170 to 190 degrees. .
- the film thickness of the phase shift film 16 is appropriately determined according to the material to be used and the design value of the reflectance, and so that the phase difference is within the above range.
- the material of the phase shift film 16 is not particularly limited as long as it has a function of absorbing EUV light and can be removed by etching or the like. In this embodiment, from the viewpoint of etching selectivity and the like.
- a tantalum material containing tantalum alone or tantalum is used, TaB alloy containing Ta and B, TaSi alloy containing Ta and Si, Ta containing Ta and other transition metals (for example, Pt, Pd, Ag). It may be an alloy, a tantalum compound obtained by adding N, O, H, C, or the like to Ta metal or an alloy thereof.
- the phase shift film 16 composed of such tantalum or a tantalum compound can be formed by a known method such as a sputtering method such as a DC sputtering method or an RF sputtering method.
- the crystal state of the phase shift film 16 is preferably an amorphous or microcrystalline structure from the viewpoint of smoothness. If the phase shift film 16 is not smooth, the edge roughness of the phase shift film pattern increases, and the dimensional accuracy of the pattern may deteriorate.
- the preferred surface roughness of the phase shift film 16 is 0.5 nm RMS or less, more preferably 0.4 nm RMS or less, and 0.3 nm RMS or less.
- Ta has a large EUV light absorption coefficient, and can be easily dry-etched with a chlorine-based gas or a fluorine-based gas. Therefore, Ta is a phase shift film material with excellent workability. Further, by adding B, Si, Ge or the like to Ta, an amorphous material can be easily obtained, and the smoothness of the phase shift film 16 can be improved. Further, if N or O is added to Ta, the resistance to oxidation of the phase shift film 16 is improved, so that it is possible to improve the stability over time.
- the phase shift film 16 includes not only one formed by a single tantalum material layer but also one formed by lamination with another material layer. . Specifically, it is a chromium-based material layer and a ruthenium-based material layer, and the chromium-based material is Cr alone, Cr alloy containing Cr and other transition metals (for example, Pt, Pd, Ag), Cr metal or Cr alloy. It may be a chromium-based compound in which N, O, H, C or the like is added.
- the ruthenium-based material may be a simple Ru metal or a Ru alloy containing Ru in a metal such as Nb, Zr, Y, B, Ti, La, Mo, Co, and Re. Further, a ruthenium compound obtained by adding N, O, H, C or the like to Ru metal or an alloy thereof may be used.
- the phase shift film 16 is formed by a laminated structure of a tantalum material layer and another material layer (when another material layer is laminated on the tantalum material layer), the film formation starts and ends. It is preferable to form a film continuously without exposure to the atmosphere. Thus, an oxide layer (tantalum oxide layer) can be prevented from being formed on the surface of the tantalum material layer 161 (a step for removing the tantalum oxide layer is not required).
- the order and number of layers of the tantalum-based material layer and the chromium-based material layer in the phase shift film 16 are not particularly limited.
- the material adjacent to the diffusion preventing layer 15 is more preferably a tantalum material layer, and the outermost surface layer of the phase shift film 16 is a chromium material layer. Is more preferable. This is because the chromium-based material layer can also have a function as an anti-oxidation film for the tantalum-based material layer (Ta is the uppermost layer, which prevents this from being oxidized and lowering the etching rate). .
- a material containing carbon specifically, CrC, CrCO, CrCN, CrCON, CrCH , CrCOH, CrCHN, CrCONH are more preferable.
- Ta and Cr include nitrides, oxides, and alloys in addition to single metals, and are not necessarily the same material and composition.
- the order and number of layers of the tantalum-based material layer and the ruthenium-based material layer in the phase shift film 16 are not particularly limited.
- a two-layer structure of Ta / Ru and a three-layer structure of Ta / Ru / Ta from the substrate 12 side. A Ta / Ru / Ta / Ru four-layer structure, a Ta / Ta / Ru / Ru four-layer structure, or the like.
- the material adjacent to the diffusion preventing layer 15 is more preferably a tantalum material layer, and the outermost surface layer of the phase shift film 16 is a ruthenium material layer. Is more preferable.
- the ruthenium-based material layer can also have a function as an antioxidant film for the tantalum-based material layer.
- Ta and Ru include nitrides, oxides, and alloys in addition to single metals, and are not necessarily the same material and composition.
- a tantalum-based material layer, a ruthenium-based material layer, and a chromium-based material layer may be stacked, and the stacking order and the number of stacked layers are not particularly limited.
- a three-layer structure of Ta / Ru / Cr, a three-layer structure of Ta / Cr / Ru may be used from the substrate 12 side, or other than these.
- ⁇ Diffusion prevention layer >> In the present invention, even when the exposure light source of the EUV exposure machine is increased in power, between the Ru-based protective film 14 of the reflective mask and the material of the phase shift film pattern (phase shift film 16) adjacent thereto, The purpose is to suppress the occurrence of interdiffusion due to thermal diffusion and thereby the reflectance with respect to EUV light fluctuates. As a means for solving this, on the surface of the Ru-based protective film 14 or The diffusion prevention layer 15 is provided on the side in contact with the phase shift film 16 as a part of the Ru-based protective film 14.
- reflection of EUV light is suppressed by suppressing mutual diffusion due to thermal diffusion between the protective film and the phase shift film even in an environment where the exposure light source of the EUV exposure machine has high power.
- the decrease in the rate is suppressed, and the reduction of the phase shift effect is suppressed even when the reflective mask is repeatedly used.
- the diffusion prevention layer 15 is formed of a material containing ruthenium (Ru) and oxygen (O), and may contain Ru and O. In addition, N or H may be contained. Ru may be a single Ru metal or a Ru alloy (preferably the same material system as the protective film material).
- examples of the material of the diffusion preventing layer 15 include RuO and RuON.
- examples of the material of the diffusion prevention layer 15 include RuNbO and RuNbON.
- the ratio (atomic%) of ruthenium (Ru) and oxygen (O) in the diffusion preventing layer 15 is 0.8 when Ru is 1. It is desirable that it is not less than 2.2 and not more than 1.0, preferably not less than 1.0 and not more than 2.0.
- the diffusion prevention layer 15 can be formed / generated by sputtering (ion beam sputtering, DC sputtering, RF sputtering) or the surface of the Ru-based protective film 14 is annealed in the atmosphere, oxygen gas, or ozone gas atmosphere. By doing so, the diffusion preventing layer may be generated.
- sputtering ion beam sputtering, DC sputtering, RF sputtering
- group protective film 14 by sputtering method although the material of the said illustration etc. can be selected freely and the diffusion prevention layer 15 can be formed, the surface of Ru type
- an oxide film or the like based on the material of the Ru-based protective film 14 is formed.
- a diffusion preventing layer 15 is newly stacked on the Ru-based protective film 14 (the film thickness is increased).
- the entire film thickness is not increased, and a part of the Ru-based protective film 14 (side in contact with the phase shift film 16) has the function of the diffusion preventing layer 15.
- the film thickness of the diffusion preventing layer 15 is preferably 0.2 nm or more and 1.5 nm or less from the viewpoint of the effect of suppressing thermal diffusion and the reflectance characteristics with respect to EUV light. If it is less than 0.2 nm, the effect of suppressing thermal diffusion is not sufficiently exhibited, which is not preferable, and if it exceeds 1.5 nm, the reflectance for EUV light is less than 63%, which is not preferable. More preferably, they are 0.3 nm or more and 1.2 nm or less, More preferably, they are 0.5 nm or more and 1.0 nm or less.
- a back surface conductive film 11 for electrostatic chuck is formed on the back surface side of the substrate 12 (on the opposite side of the surface on which the multilayer reflective film 13 is formed).
- the electrical characteristics required for the back surface conductive film 11 for the electrostatic chuck are usually 100 ⁇ / sq or less.
- the back surface conductive film 11 can be formed by, for example, magnetron sputtering or ion beam sputtering using a metal or alloy target such as chromium or tantalum.
- the thickness of the back conductive film 11 is not particularly limited as long as it satisfies the function for an electrostatic chuck, but is usually 10 to 200 nm.
- the reflective mask blank 10 of the present embodiment has been described for each layer.
- the reflective mask blank may include an etching mask film or a resist film on the phase shift film 16.
- a typical material for the etching mask film a material obtained by adding oxygen, nitrogen, carbon, or hydrogen to silicon (Si) or silicon (Si) can be used. Specific examples include Si, SiO, SiN, SiON, SiC, SiCO, SiCN, and SiCON.
- the formation of an etching mask film makes it possible to reduce the thickness of the resist film, which is advantageous for pattern miniaturization.
- the material of the outermost surface layer of the phase shift film 16 is a material that is etched with a chlorine-based gas (which may contain oxygen)
- the material of the etching mask film has resistance to the chlorine-based gas.
- the material of the etching mask film is: A material that is resistant to fluorine-based gas and that can be etched with respect to chlorine-based gas (which may contain oxygen) is selected. In this case, from the viewpoint of thinning the resist film, it is preferable to select a material that can be etched with respect to a chlorine-based gas not containing oxygen.
- a reflective mask can be produced using the reflective mask blank 10 of the present embodiment described above.
- a photolithography method that can perform high-definition patterning is most suitable.
- a chlorine-based gas such as Cl 2 , SiCl 4 , CHCl 3 , CCl 4 , a mixed gas containing these chlorine-based gas and O 2 in a predetermined ratio, a chlorine-based gas, and He are in a predetermined ratio.
- etching with an etching gas suitable for each material is performed a plurality of times.
- a reflective mask for EUV lithography that achieves high reflectance.
- wet cleaning using an acidic or alkaline aqueous solution is performed to obtain a reflective mask for EUV lithography that achieves high reflectance.
- the resist film is also removed at the same time. There is a case where a process only for removing is unnecessary.
- a process for removing the etching mask film may be separately required.
- a transfer pattern based on the phase shift film pattern of the reflective mask is formed on the semiconductor substrate by lithography, and various other processes are performed on the semiconductor substrate.
- a semiconductor device in which the pattern or the like is formed can be manufactured.
- a pattern transfer device (exposure device) 50 shown in FIG. 6 transfers a pattern to the semiconductor substrate with a resist film (transfer target substrate) 30 by EUV light using the reflective mask of this embodiment. A method will be described.
- the pattern transfer apparatus 50 equipped with the reflective mask 20 of the present embodiment includes a laser plasma X-ray source (exposure light source) 31, a reflective mask 20, a reduction optical system 32, and the like.
- a laser plasma X-ray source (exposure light source) 31 As the reduction optical system 32, an X-ray reflection mirror is used.
- a laser plasma X-ray source (exposure light source) 31 As the laser plasma X-ray source (exposure light source) 31, a laser plasma X-ray source (exposure light source) 31 having a power of 80 W or more is used from the viewpoint of optimizing the throughput.
- the pattern reflected by the reflective mask 20 is usually reduced to about 1 ⁇ 4 by the reduction optical system 32.
- a wavelength band of 13 to 14 nm is used as the exposure wavelength, and the optical path is preset so as to be in a vacuum.
- EUV light obtained from the laser plasma X-ray source 31 is incident on the reflective mask 20, and the light reflected here is transferred onto the semiconductor substrate 30 with a resist film through the reduction optical system 32 (see FIG.
- the transfer pattern is transferred to a resist film formed on the transfer substrate).
- the EUV light incident on the reflective mask 20 is not absorbed and reflected by the phase shift film 16 in the portion where the phase shift film 16 remains, while the multilayer reflective film is formed in the portion where the phase shift film 16 does not remain. EUV light is incident on 13 and reflected. In this way, an image formed by the light reflected from the reflective mask 20 enters the reduction optical system 32, and the exposure light passing through the reduction optical system 32 is applied to the resist layer on the semiconductor substrate 30 with a resist film.
- the phase shift film 16 reflects a part of the EUV light, and the phase of this light is shifted by 180 degrees with respect to the light reflected from the multilayer reflective film 13. Increasing the contrast of the image).
- a resist pattern can be formed on the semiconductor substrate 30 with a resist film. Then, by performing etching or the like using this resist pattern as a mask, for example, a predetermined wiring pattern can be formed on the semiconductor substrate. A semiconductor device is manufactured through such a process and other necessary processes.
- FIG. 2 is a schematic diagram showing a process of producing a reflective mask for EUV lithography from the reflective mask blank for EUV lithography according to the first embodiment.
- the reflective mask blank 10 of Example 1 includes a back conductive film 11, a substrate 12, a multilayer reflective film 13, a Ru-based protective film 14, a diffusion prevention layer 15, And a phase shift film 16.
- the phase shift film 16 is formed of a tantalum-based material layer 161 and a chromium-based material layer 162 (laminated from the bottom in this order), and an etching mask film 17 is formed on the phase shift film 16.
- the multilayer reflective film 13 was formed on the main surface of the substrate 12 opposite to the side on which the back conductive film 11 was formed.
- the multilayer reflective film 13 formed on the substrate 12 is a Mo / Si periodic multilayer reflective film in order to obtain a multilayer reflective film suitable for 13.5 nm EUV light.
- the multilayer reflective film 13 was formed by alternately stacking Mo layers and Si layers on the substrate 12 by ion beam sputtering (Ar gas atmosphere) using a Mo target and a Si target. First, a Si film was formed with a thickness of 4.2 nm, and then a Mo film was formed with a thickness of 2.8 nm. This was taken as one period, and 40 periods were laminated in the same manner. Finally, a Si film was formed to a thickness of 4.0 nm, and a multilayer reflective film 13 was formed.
- a RuNb protective film 14 having a thickness of 2.5 nm was formed by ion beam sputtering (Ar gas atmosphere) using a RuNb (Ru: 80 at%, Nb: 20 at%) target.
- the diffusion preventing layer 15 of RuO 2 (film thickness 1.0 nm) was formed on the side of the Ru-based protective film 14 in contact with the phase shift film 16. That is, a part of the Ru-based protective film 14 has the function of the diffusion preventing layer 15 (the surface layer side 1.0 nm of the 2.5 nm Ru-based protective film 14 functions as the diffusion preventing layer 15).
- TaN film tantalum-based material layer 161
- CrCON film chromium-based material layer 162
- the TaN film is a tantalum target, and a 5 nm-thick TaN film (Ta: 92.5 at%, N: 7.5 at%) is formed by a reactive sputtering method in a mixed gas atmosphere of Ar gas and N 2 gas. did.
- the CrCON film is a chromium target, and a 46 nm-thick CrCON film (Cr: 45 at%, C: 10 at%, O: 35) is formed by reactive sputtering in a mixed gas atmosphere of Ar gas, CO 2 gas, and N 2 gas. (at%, N: 10 at%) was formed (continuous film formation from the TaN film to the CrCON film without exposure to the atmosphere).
- the refractive index, n, and extinction coefficient k at a wavelength of 13.5 nm of the formed TaN film and CrCON film were as follows.
- TaN n ⁇ 0.94, k ⁇ 0.034 CrCON: n ⁇ 0.93, k ⁇ 0.037
- the film thicknesses of the TaN film and the CrCON film are set so that the reflectance is 2% and the phase difference is 180 degrees at a wavelength of 13.5 nm.
- the reflective mask blank 10 of Example 1 was obtained as described above.
- the reflectance of EUV light on the surface of the phase shift film was measured in the state of a reflective mask blank (without an etching mask film) produced by the same production method as described above, it was 2.5%.
- heat treatment is performed at 80 ° C. for 1 hour in a vacuum, and reflection of EUV light on the surface of the phase shift film after the heat treatment is performed.
- the rate was measured, it was almost unchanged at 2.4%. This is presumed that thermal diffusion between the Ru-based protective film 14 and the phase shift film 16 is suppressed by the diffusion preventing layer 15.
- the diffusion prevention layer 15 according to the present invention is formed, thermal diffusion between the protective film and the phase shift film is suppressed even in an environment where the exposure light source is used with high power. Therefore, it is possible to obtain a reflective mask in which the decrease is suppressed, and thus the decrease in the phase effect is suppressed.
- the tantalum-based material layer 161 is formed adjacent to the diffusion preventing layer 15 as in this embodiment.
- the tantalum material layer 161 is formed adjacent to the diffusion prevention layer 15 to protect the tantalum material layer 161 when it is patterned. It is preferable in that a reflective mask with high reflectivity can be obtained with little damage to the film / diffusion prevention film.
- the etching gas used when patterning the chromium-based material layer 162 is a mixed gas of chlorine and oxygen (Cl 2 + O 2 ). This is because the Ru-based protective film is eroded.
- the phase shift film 16 is formed as a laminated film continuously formed without being exposed to the atmosphere from the start of film formation to the end of film formation by a sputtering method.
- an oxide layer (tantalum oxide layer) can be prevented from being formed on the surface of the layer 161. That is, when a tantalum-based material layer is included as a material for the phase shift film, a tantalum oxide layer is formed on the surface of the layer when exposed to the atmosphere.
- the tantalum oxide layer cannot be etched unless a fluorine-based gas is used as an etching gas, and the process is complicated, which is not preferable (the chromium-based material layer can be etched with a mixed gas of chlorine and oxygen even if the surface is oxidized).
- the outermost surface layer of the phase shift film 16 is preferably a chromium-based material layer (the outermost-layer chromium-based material layer has a function as an antioxidant layer).
- a resist film 18 is formed to a thickness of 40 nm on the etching mask film 17 of the reflective mask blank 10 (FIG. 2B), and a desired pattern is drawn (exposure) on the resist film, followed by development and rinsing. Thus, a predetermined resist film pattern 18a is formed.
- the SiO 2 film is dry-etched with a fluorine-based gas (CF 4 gas) to form an etching mask film pattern 17a (FIG. 2C).
- CF 4 gas fluorine-based gas
- the reflective mask 20 of the present embodiment since the thermal diffusion between the protective film and the phase shift film is suppressed even when the exposure light source is used in a high power environment, the reflectance of the EUV light is reduced. Therefore, even if it is repeatedly used, the decrease in the phase effect is suppressed, so that a stable semiconductor device can be manufactured, which is very useful.
- the outermost surface layer is the chromium-based material layer 162 containing carbon, and therefore has mask cleaning resistance (resistance to a cleaning liquid (for example, an acid-based cleaning liquid) that removes residual carbon). It is also useful in terms. Reflective masks are usually used in an environment without a pellicle.
- the chromium-based material layer may further contain oxygen, nitrogen, hydrogen, or the like.
- the etching mask film 17 is formed on the phase shift film 16, so that the resist film 18 for forming a transfer pattern can be thinned, and a fine pattern can be formed.
- a reflective mask is obtained. That is, when the etching mask film 17 is not present, the resist film pattern 18a is also etched by the Cl 2 + O 2 gas containing O 2 when the chromium-based material layer 162 is etched (FIG. 2 (c) ⁇ (d)). Therefore, it is necessary to increase the thickness of the resist film 18 (generally, the resist layer needs to be about three times as thick as the Cr layer), but if the resist film pattern 18a becomes too high, the resist film 18 may collapse.
- the resist film 18 can be thinned.
- FIG. 3 is a schematic diagram showing a process of producing a reflective mask for EUV lithography from a reflective mask blank for EUV lithography according to the second embodiment.
- Example 2 is different from Example 1 in that the TaN film (tantalum-based material layer 161) and the CrCON film (chromium-based material layer 162) in the phase shift film have thicknesses of 27 nm and 25 nm, respectively, and an etching mask film is used. Except not formed (if the thickness of the chromium-based material layer 162 is equal to or less than a certain value, the resist film 18 is within a range that can be dealt with (in this embodiment, the resist film 18 has a thickness of 80 nm). In the same manner as in Example 1, a reflective mask blank and a reflective mask were produced.
- the step of etching the etching mask film with a fluorine-based gas is not necessary, and on the other hand, the step of finally etching the resist film pattern 18a with an oxygen-based gas is required (FIG. 3D ⁇ ( e)).
- the film thicknesses of the TaN film (tantalum-based material layer 161) and CrCON film (chromium-based material layer 162) are set so that the reflectance is 2% and the phase difference is 180 degrees at a wavelength of 13.5 nm. It is.
- FIG. 4 is a schematic diagram showing a process of producing a reflective mask for EUV lithography from the reflective mask blank for EUV lithography in Example 3.
- the phase shift film 16 of Example 1 is a TaN film (tantalum-based material layer 161) and a CrCON film (chromium-based material layer 162), whereas the phase shift film 16 is replaced with a TaN film (tantalum-based material).
- the layer 161) and the Ru film (ruthenium-based material layer 163) are formed in this order, and the film thicknesses are 5 nm and 27 nm, respectively.
- the phase shift film 16 was formed by stacking a TaN film (tantalum-based material layer 161) and a Ru film (ruthenium-based material layer 163) by DC sputtering.
- the TaN film is a tantalum target, and a 5 nm-thick TaN film (Ta: 92.5 at%, N: 7.5 at%) is formed by a reactive sputtering method in a mixed gas atmosphere of Ar gas and N 2 gas. did.
- the Ru film was a ruthenium target, and a Ru film having a film thickness of 27 nm was formed by sputtering in an Ar gas atmosphere (continuous film formation from the TaN film to the Ru film without being exposed to the atmosphere).
- the refractive index, n, and extinction coefficient k at a wavelength of 13.5 nm of the formed TaN film and Ru film were as follows.
- the film thicknesses of the TaN film and the Ru film are set so that the reflectance is 26% and the phase difference is 180 degrees at a wavelength of 13.5 nm.
- the CrCON film chromium-based material layer 162 as the phase shift film in Example 1 is used.
- the Ru film ruthenium-based material layer 163 is used.
- the etching process using the resist film pattern 18a and the etching mask film pattern 17a as a mask (FIG. 4 (c) ⁇ (d))
- the Ru film is dry-etched with O 2 gas.
- the others are the same as in the first embodiment.
- the resist film 18 is removed during dry etching of the Ru film with O 2 gas.
- the Ru film (ruthenium-based material layer 163) is used in the phase shift film 16
- the entire thickness of the phase shift film 16 can be reduced (in the comparative example described later, the phase shift is performed).
- the film is 58 nm
- Example 1 is 51 nm
- Example 2 is 52 nm, compared to 32 nm in this example and 40 nm in Example 4.
- FIG. 5 is a schematic diagram showing a process of producing a reflective mask for EUV lithography from a reflective mask blank for EUV lithography in Example 4.
- Example 4 is the same as Example 3 except that the film thicknesses of the TaN film (tantalum-based material layer 161) and the Ru film (ruthenium-based material layer 163) in the phase shift film were 24 nm and 16 nm, respectively.
- a reflective mask blank and a reflective mask were produced.
- the film thicknesses of the TaN film and the Ru film are set so that the reflectance is 6% and the phase difference is 180 degrees at a wavelength of 13.5 nm.
- the reflectance of EUV light on the surface of the phase shift film in the state of a reflective mask blank (without an etching mask film) produced by the same method as described above was 6.2%.
- heat treatment is performed at 80 ° C. for 1 hour in a vacuum, and reflection of EUV light on the surface of the phase shift film after the heat treatment is performed.
- the rate was measured, it was 6.1%. Similar to Example 1, the result that there was almost no change in the reflectance was obtained.
- Example 5 a diffusion prevention layer is formed as compared with Example 1, and a Ru protective film 14 having a thickness of 1.5 nm is formed by DC sputtering using an Ru target in an Ar gas atmosphere, and then an Ar + O2 mixed gas is formed.
- a reflective mask in the same manner as in Example 1 except that a RuO 2 diffusion prevention film 15 (composition ratio Ru: O 1: 2) having a thickness of 1.0 nm was formed by DC sputtering using a Ru target in an atmosphere. A blank and a reflective mask blank were produced.
- the reflectance of EUV light on the surface of the phase shift film in a state of a reflective mask blank (without an etching mask film) produced by the same method as described above was 2.0%.
- heat treatment is performed at 80 ° C. for 1 hour in a vacuum, and reflection of EUV light on the surface of the phase shift film after the heat treatment is performed.
- the rate was measured, it was 2.1%. Similar to Example 1, the result that there was almost no change in the reflectance was obtained.
- FIG. 7 is a schematic diagram showing a process of manufacturing a reflective mask for EUV lithography from a conventional reflective mask blank for EUV lithography which is a comparative example.
- the TaN film (phase shift film 160) is formed to 58 nm by DC sputtering without providing the diffusion prevention layer 15 on the Ru-based protective film 14 (or as a part of the Ru-based protective film 14). Filmed. At this time, the thickness of the TaN film is set so that the reflectance is 3% and the phase difference is 180 degrees.
- the reflective mask blank of this embodiment (and the reflective mask manufactured thereby), diffusion prevention containing ruthenium and oxygen on the side of the Ru-based protective film 14 in contact with the phase shift layer 16 is prevented. Since the layer 15 is formed, the heat diffusion of the protective film and the phase shift film (absorber film) is suppressed even under the use environment where the exposure light source of the EUV exposure machine is high power, thereby reducing the reflectance of the EUV light. The reduction is suppressed, and even if the reflective mask is used repeatedly, the phase shift effect is suppressed from being reduced (significant difference is obtained even when compared with the conventional example).
- the total thickness of the resist film to the phase shift film is 158 nm (resist film: 100 nm, phase shift film: 58 nm), whereas in the example, it can be formed thinner (Example 1: 96 nm (Example 1: Resist film: 40 nm, etching mask film: 5 nm, phase shift film: 51 nm), Example 2: 132 nm (resist film: 80 nm, phase shift film: 52 nm), Example 3: 77 nm (resist film: 40 nm, etching mask film) : 5 nm, phase shift film: 32 nm), Example 4: 85 nm (resist film: 40 nm, etching mask film: 5 nm, phase shift film: 40 nm)), which is advantageous in forming fine patterns.
- the uppermost layer of the multilayer reflective film 13 is formed of silicon (Si), and a silicon oxide layer containing silicon and oxygen is formed between the uppermost layer (Si) and the Ru-based protective film 14. May be.
- a protective film is provided on the multilayer reflective film, Si diffuses into the Ru-based protective film between the Si layer and the protective film, and further undergoes oxidation to form silicon oxide. Film peeling occurs due to repeated cleaning in the mask manufacturing process and use after the product is completed.
- a silicon oxide layer containing silicon and oxygen between the uppermost Si of the multilayer reflective film 13 and the Ru-based protective film 14 are formed.
- the thickness of the silicon oxide layer is preferably 0.2 nm or more from the viewpoint of suppressing the migration of Si to the protective film. Moreover, 3 nm or less is preferable from a viewpoint of suppression of the reflectance fall of EUV light. A more preferable range based on both viewpoints is 0.5 to 2 nm.
- the silicon oxide layer can be formed by an ion beam sputtering method, a sputtering method, a CVD, a vacuum deposition method, or the like, and the silicon (Si) that is the uppermost layer of the multilayer reflective film 13 is annealed to form A silicon oxide layer may be formed on the surface layer of the upper silicon layer.
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Abstract
Description
基板上に多層反射膜と、保護膜と、EUV光の位相をシフトさせる位相シフト膜がこの順に形成された反射型マスクブランクであって、前記保護膜は、ルテニウムを主成分として含む材料からなり、前記位相シフト膜は、タンタルを含むタンタル系材料層を有し、前記保護膜表面上に、又は、前記保護膜の一部として前記位相シフト層と接する側に、前記位相シフト膜との相互拡散を抑止するルテニウムと酸素とを含む拡散防止層が形成されていることを特徴とする反射型マスクブランク。
前記タンタル系材料層が前記拡散防止層と隣接していることを特徴とする構成1記載の反射型マスクブランク。
前記拡散防止層の膜厚は0.2nm以上1.5nm以下であることを特徴とする構成1又は2に記載の反射型マスクブランク。
前記位相シフト膜は積層構造で形成され、最表面層がクロム系材料層であることを特徴とする構成1乃至構成3の何れか1つに記載の反射型マスクブランク。
前記クロム系材料層は、炭素を含むことを特徴とする構成4記載の反射型マスクブランク。
前記位相シフト膜は積層構造で形成され、最表面層がルテニウム系材料層であることを特徴とする構成1乃至構成3の何れか1つに記載の反射型マスクブランク。
前記位相シフト膜はスパッタリング法にて成膜され、成膜開始から成膜終了まで大気に曝されず連続して成膜された積層構造を有することを特徴とする構成1乃至構成6に記載の反射型マスクブランク。
前記位相シフト膜上に、エッチングマスク膜が形成されていることを特徴とする構成1乃至構成7に記載の反射型マスクブランク。
前記多層反射膜の最上層は、ケイ素(Si)であって、前記最上層と前記保護膜との間に、ケイ素と酸素とを含むケイ素酸化物層を有することを特徴とする構成1乃至構成8の何れか1つに記載の反射型マスクブランク。
構成1乃至9のいずれか一つに記載の反射型マスクブランクによって作製されることを特徴とする反射型マスク。
EUV光を発する露光光源を有する露光装置に、構成10記載の反射型マスクをセットし、被転写基板上に形成されているレジスト膜に転写パターンを転写する工程を有することを特徴とする半導体装置の製造方法。
前記露光光源のパワー(電力)は、80W以上であることを特徴とする構成11記載の半導体装置の製造方法。
図1は、本発明に係るEUVリソグラフィ用反射型マスクブランクの構成を説明するための概略図である。同図に示されるように、反射型マスクブランク10は、基板12と、露光光であるEUV光を反射する多層反射膜13と、当該多層反射膜13を保護するためのルテニウムを主成分とした材料で形成されるRu系保護膜14と、ルテニウムと酸素とを含む材料で形成される拡散防止層15と、EUV光を吸収するとともに一部のEUV光を反射し、その位相をシフトさせるための位相シフト膜16と、を有し、これらがこの順で積層されるものである。また、基板12の裏面側には、静電チャック用の裏面導電膜11が形成される。
基板12は、EUV光による露光時の熱による吸収体膜パターンの歪みを防止するため、0±5ppb/℃の範囲内の低熱膨張係数を有するものが好ましく用いられる。この範囲の低熱膨張係数を有する素材としては、例えば、SiO2-TiO2系ガラス、多成分系ガラスセラミックス等を用いることができる。
多層反射膜13は、EUVリソグラフィ用反射型マスクにおいて、EUV光を反射する機能を付与するものであり、屈折率の異なる元素が周期的に積層された多層膜の構成となっている。
Ru系保護膜14は、後述するEUVリソグラフィ用反射型マスクの製造工程におけるドライエッチングや洗浄から多層反射膜13を保護するために、多層反射膜13の上に形成される。Ru系保護膜14は、ルテニウムを主成分として含む材料(主成分:50at%以上)により構成され、Ru金属単体でもよいし、RuにNb、Zr、Y、B、Ti、La、Mo、Co、Reなどの金属を含有したRu合金であってよく、窒素を含んでいても構わない。また、Ru系保護膜14を3層以上の積層構造とし、最下層と最上層を、上記Ruを含有する物質からなる層とし、最下層と最上層との間に、Ru以外の金属、若しくは合金を介在させたものとしても構わない。
本発明は、EUV露光機の露光光源が高パワー化した場合においても、反射型マスクのRu系保護膜14とこれに隣接する位相シフト膜パターン(位相シフト膜16)の材料との間で、熱拡散による相互拡散が生じ、これによってEUV光に対する反射率が変動してしまうことを抑止することを目的としており、これを解決するための手段として、Ru系保護膜14の表面上に、又は、Ru系保護膜14の一部として位相シフト膜16と接する側に、拡散防止層15が備えられるものである。拡散防止層15が形成されることによって、EUV露光機の露光光源が高パワーである使用環境下でも保護膜と位相シフト膜の間における熱拡散による相互拡散が抑制されることによりEUV光の反射率の低下が抑制され、反射型マスクが繰り返し使用されても位相シフト効果が低減することが抑止されるものである。
基板12の裏面側(多層反射膜13の形成面の反対側)には、静電チャック用の裏面導電膜11が形成される。静電チャック用の裏面導電膜11に求められる電気的特性は通常100Ω/sq以下である。裏面導電膜11の形成方法は、例えばマグネトロンスパッタリング法やイオンビームスパッタ法により、クロム、タンタル等の金属や合金のターゲットを使用して形成することができる。裏面導電膜11の厚さは、静電チャック用としての機能を満足する限り特に限定されないが、通常10~200nmである。
上記説明した本実施形態の反射型マスクブランク10を使用して、反射型マスクを作製することができる。EUVリソグラフィ用反射型マスクの製造には、高精細のパターニングを行うことができるフォトリソグラフィー法が最も好適である。
上記本実施形態の反射型マスクを使用して、リソグラフィ技術により半導体基板上に反射型マスクの位相シフト膜パターンに基づく転写パターンを形成し、その他種々の工程を経ることで、半導体基板上に種々のパターン等が形成された半導体装置を製造することができる。
先ず、実施例1のマスクブランク10について説明する。
(((裏面導電膜)))
SiO2-TiO2系ガラス基板12の裏面にCrNからなる裏面導電膜11をマグネトロンスパッタリング法により下記の条件にて形成した。
裏面導電膜形成条件:Crターゲット、Ar+N2ガス雰囲気(Ar:N2:90%:N:10%)、膜厚20nm。
次に、裏面導電膜11が形成された側と反対側の基板12の主表面上に、多層反射膜13を形成した。基板12上に形成される多層反射膜13は、13.5nmのEUV光に適した多層反射膜とするために、Mo/Si周期多層反射膜を採用した。多層反射膜13は、MoターゲットとSiターゲットを使用し、イオンビームスパッタリング(Arガス雰囲気)により基板12上にMo層およびSi層を交互に積層して形成した。まず、Si膜を4.2nmの厚みで成膜し、続いて、Mo膜を2.8nmの厚みで成膜した。これを一周期とし、同様にして40周期積層し、最後にSi膜を4.0nmの厚みで成膜し、多層反射膜13を形成した。
引き続き、RuNb(Ru:80at%、Nb:20at%)ターゲットを使用したイオンビームスパッタリング(Arガス雰囲気)によりRuNb保護膜14を2.5nmの厚みで成膜した。
次に、Ru系保護膜14の表面に高濃度オゾンガス処理を行った。この場合のオゾンガスの濃度は100体積%とし、処理時間は10分、多層反射膜付き基板を60度に加熱した。これにより、Ru系保護膜14の位相シフト膜16と接する側に、RuO2(膜厚1.0nm)の拡散防止層15を形成した。即ち、Ru系保護膜14の一部が拡散防止層15の機能を有することになる(2.5nmのRu系保護膜14の内の表層側1.0nmが拡散防止層15として機能する)。
次に、DCスパッタリングによりTaN膜(タンタル系材料層161)とCrCON膜(クロム系材料層162)を積層して、位相シフト膜16を形成した。TaN膜は、タンタルターゲットとし、ArガスとN2ガスの混合ガス雰囲気にて反応性スパッタリング法で膜厚5nmのTaN膜(Ta:92.5 at%、N:7.5 at%) を形成した。CrCON膜は、クロムターゲットとし、ArガスとCO2ガスとN2ガスの混合ガス雰囲気にて反応性スパッタリングで膜厚46nmのCrCON膜(Cr:45 at%、C:10 at%、O:35 at%、N:10 at%) を形成した(TaN膜からCrCON膜の形成まで大気に触れさせず連続成膜)。
上記形成したTaN膜とCrCON膜の波長13.5nmにおける屈折率、n、消衰係数kは、それぞれ以下であった。
TaN:n→0.94、k→0.034
CrCON:n→0.93、k→0.037
なお、上記、TaN膜とCrCON膜の膜厚は、波長13.5nmにおいて反射率が2%、位相差が180度となるように設定してある。
次に、位相シフト膜16上にエッチングマスク膜17であるSiO2膜をRFスパッタリングにより膜厚5nmで形成した。
次に、上記反射型マスクブランク10を用いて、反射型マスク20を作製した。
TaN:n→0.94、k→0.034
Ru:n→0.888、k→0.017
なお、上記、TaN膜とRu膜の膜厚は、波長13.5nmにおいて反射率が26%、位相差が180度となるように設定してある。
図7は、比較例である従来のEUVリソグラフィ用反射型マスクブランクからEUVリソグラフィ用反射型マスクを作製する工程を示す模式図である。
Claims (12)
- 基板上に多層反射膜と、保護膜と、EUV光の位相をシフトさせる位相シフト膜がこの順に形成された反射型マスクブランクであって、
前記保護膜は、ルテニウムを主成分として含む材料からなり、
前記位相シフト膜は、タンタルを含むタンタル系材料層を有し、
前記保護膜表面上に、又は、前記保護膜の一部として前記位相シフト層と接する側に、前記位相シフト膜との相互拡散を抑止するルテニウムと酸素とを含む拡散防止層が形成されていることを特徴とする反射型マスクブランク。 - 前記タンタル系材料層が前記拡散防止層と隣接していることを特徴とする請求項1に記載の反射型マスクブランク。
- 前記拡散防止層の膜厚は0.2nm以上1.5nm以下であることを特徴とする請求項1又は請求項2に記載の反射型マスクブランク。
- 前記位相シフト膜は積層構造で形成され、最表面層がクロム系材料層であることを特徴とする請求項1乃至請求項3の何れか1つに記載の反射型マスクブランク。
- 前記クロム系材料層は、炭素を含むことを特徴とする請求項4に記載の反射型マスクブランク。
- 前記位相シフト膜は積層構造で形成され、最表面層がルテニウム系材料層であることを特徴とする請求項1乃至請求項3の何れか1つに記載の反射型マスクブランク。
- 前記位相シフト膜はスパッタリング法にて成膜され、成膜開始から成膜終了まで大気に曝されず連続して成膜された積層構造を有することを特徴とする請求項1乃至請求項6に記載の反射型マスクブランク。
- 前記位相シフト膜上に、エッチングマスク膜が形成されていることを特徴とする請求項1乃至請求項7に記載の反射型マスクブランク。
- 前記多層反射膜の最上層は、ケイ素(Si)であって、前記最上層と前記保護膜との間に、ケイ素と酸素とを含むケイ素酸化物層を有することを特徴とする請求項1乃至請求項8の何れか1つに記載の反射型マスクブランク。
- 請求項1乃至9のいずれか一項に記載の反射型マスクブランクによって作製されることを特徴とする反射型マスク。
- EUV光を発する露光光源を有する露光装置に、請求項10に記載の反射型マスクをセットし、被転写基板上に形成されているレジスト膜に転写パターンを転写する工程を有することを特徴とする半導体装置の製造方法。
- 前記露光光源のパワー(電力)は、80W以上であることを特徴とする請求項11記載の半導体装置の製造方法。
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KR102331865B1 (ko) | 2021-11-29 |
US20170038673A1 (en) | 2017-02-09 |
TW201525607A (zh) | 2015-07-01 |
US20180120692A1 (en) | 2018-05-03 |
US9864267B2 (en) | 2018-01-09 |
JP2015122468A (ja) | 2015-07-02 |
KR20160101920A (ko) | 2016-08-26 |
US10481484B2 (en) | 2019-11-19 |
TWI631412B (zh) | 2018-08-01 |
JP6301127B2 (ja) | 2018-03-28 |
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