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WO2024154535A1 - Ébauche de masque réfléchissant, masque réfléchissant et procédé de fabrication de masque réfléchissant - Google Patents

Ébauche de masque réfléchissant, masque réfléchissant et procédé de fabrication de masque réfléchissant Download PDF

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Publication number
WO2024154535A1
WO2024154535A1 PCT/JP2023/045963 JP2023045963W WO2024154535A1 WO 2024154535 A1 WO2024154535 A1 WO 2024154535A1 JP 2023045963 W JP2023045963 W JP 2023045963W WO 2024154535 A1 WO2024154535 A1 WO 2024154535A1
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WO
WIPO (PCT)
Prior art keywords
film
reflective mask
outermost layer
mask blank
absorber film
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PCT/JP2023/045963
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English (en)
Japanese (ja)
Inventor
広朗 伊藤
大二郎 赤木
大河 筆谷
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AGC Inc
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Asahi Glass Co Ltd
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Priority to JP2024571671A priority Critical patent/JPWO2024154535A1/ja
Publication of WO2024154535A1 publication Critical patent/WO2024154535A1/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • 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
    • 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
    • G03F1/54—Absorbers, e.g. of opaque materials
    • G03F1/58—Absorbers, e.g. of opaque materials having two or more different absorber layers, e.g. stacked multilayer absorbers

Definitions

  • the present invention relates to a reflective mask used in EUV (Etreme Ultra Violet) exposure, which is used in the exposure process of semiconductor manufacturing, a method for manufacturing the same, and a reflective mask blank, which is the original plate for the reflective mask.
  • EUV EUV
  • EUV lithography which uses EUV light with a central wavelength of around 13.5 nm as a light source, has been considered in order to further miniaturize semiconductor devices.
  • a reflective optical system and a reflective mask are used due to the characteristics of EUV light.
  • a multilayer reflective film that reflects EUV light is formed on a substrate, and an absorber film that absorbs EUV light is patterned on the multilayer reflective film.
  • the absorber film only needs to have a low reflectance of EUV light as a result, and may be formed of a material that has a high absorbance of EUV light, or may be a phase shift film.
  • a phase shift film is a film that imparts a phase difference to the transmitted EUV light, and the reflectance of EUV light is reduced by interference between the EUV lights with the phase difference.
  • a protective film is often provided between the multilayer reflective film and the absorber film for the purpose of protecting the multilayer reflective film.
  • a reflective mask is obtained, for example, by patterning the absorber film of a reflective mask blank that has, in that order, a substrate, a multilayer reflective film that reflects EUV light, a protective film, and an absorber film.
  • EUV exposure is performed using a reflective mask
  • the EUV light that is incident on the reflective mask from the illumination optical system of the exposure tool is reflected in areas where there is no absorber film (openings), and is less reflected in areas where there is an absorber film (non-openings).
  • the mask pattern is transferred as a resist pattern onto the wafer through the reduced projection optical system of the exposure tool, and subsequent processing is carried out.
  • Patent Document 1 discloses an embodiment having a multilayer reflective film, a protective film, a multilayer phase shift film, and an etching mask film on a substrate.
  • the absorber film and the film disposed on the opposite side of the protective film of the absorber film may be processed to form an alignment mark for positioning.
  • the processing of the absorber film and the film disposed on the opposite side of the protective film of the absorber film may be performed by irradiating the film disposed on the opposite side of the protective film of the absorber film with a charged particle beam such as an electron beam or an ion beam.
  • a charged particle beam such as an electron beam or an ion beam.
  • processing of the absorber film by a charged particle beam may be performed.
  • the present invention has been made in view of the above problems, and an object of the present invention is to provide a reflective mask blank which has small processing errors and excellent inspectability when processed with a charged particle beam. Another object of the present invention is to provide a reflective mask and a method for manufacturing a reflective mask.
  • the inventors discovered that the above-mentioned problems could be solved by configuring the absorber film in a reflective mask blank with a specific structure and controlling the material and thickness of the outermost layer located on the surface opposite the substrate, and thus completed the present invention.
  • the outermost layer contains nitrogen, oxygen, and tantalum, The reflective mask blank according to any one of [1] to [4], wherein the density of the outermost layer obtained by X-ray reflectivity measurement is 6.0 to 12.0 g/ cm3 .
  • the outermost layer contains at least one of nitrogen and oxygen and silicon, The reflective mask blank according to any one of [1] to [5], wherein the density of the outermost layer obtained by X-ray reflectivity measurement is 1.5 to 3.0 g/ cm3 .
  • the outermost layer contains at least one of nitrogen and oxygen and chromium
  • the reflective mask blank according to any one of [1] to [6] wherein the density of the outermost layer obtained by X-ray reflectivity measurement is 3.5 to 7.0 g/ cm3 .
  • a method for producing a reflective mask comprising a step of patterning the absorber film of the reflective mask blank according to any one of [1] to [9].
  • the present invention it is possible to provide a reflective mask blank which has small processing errors and excellent inspectability when processed with a charged particle beam.
  • the present invention also provides a reflective mask and a method for manufacturing a reflective mask.
  • FIG. 1 is a schematic diagram showing an example of a reflective mask blank of the present invention.
  • 1A to 1C are schematic diagrams showing an example of a manufacturing process for a reflective mask using the reflective mask blank of the present invention.
  • FIG. 11 is a schematic diagram for explaining a processing error in the embodiment.
  • the reflective mask blank of the present invention is a reflective mask blank having, in this order, a substrate, a multilayer reflective film that reflects EUV light, a protective film, an absorber film, and an outermost layer.
  • the absorber film contains Ru, and the oxygen content in the absorber film is 30 atomic % or less relative to all atoms in the absorber film.
  • the outermost layer is located on the outermost surface side opposite to the substrate, contains at least one element selected from the group consisting of Si, Cr, Nb, Ru, and Ta, and O, and has a film thickness of less than 4 nm.
  • a reflective mask blank 10 shown in FIG. 1 has a substrate 12, a reflective multilayer film 14, a protective film 16, an absorber film 18, and an outermost layer 20 in this order.
  • the absorber film 18 contains Ru, and the oxygen content in the absorber film 18 is 30 atomic % or less with respect to all atoms in the absorber film 18.
  • the outermost layer 20 contains O and at least one element selected from the group consisting of Si, Cr, Nb, Ru, and Ta, and the film thickness of the outermost layer 20 is less than 4 nm.
  • the film thickness of the outermost layer is less than 4 nm. If the film thickness of the outermost layer is less than 4 nm, it is considered that charges tend to move to the absorber film side before being accumulated in the outermost layer, and the outermost layer is less likely to be charged. As a result, it is presumed that the reflective mask blank of the present invention has a small processing error. It is also believed that the inclusion of O in the outermost layer reduces the reflectance of ultraviolet light from the outermost layer. The configuration of the reflective mask blank of the present invention will be described below.
  • the substrate of the reflective mask blank of the present invention preferably has a small thermal expansion coefficient.
  • a substrate with a small thermal expansion coefficient can suppress distortion of the absorber film pattern due to heat during exposure to EUV light.
  • the thermal expansion coefficient of the substrate at 20°C is preferably 0 ⁇ 1.0 ⁇ 10 -7 /°C, and more preferably 0 ⁇ 0.3 ⁇ 10 -7 /°C.
  • Materials with a small thermal expansion coefficient include SiO 2 --TiO 2 type glass, but are not limited thereto.
  • Substrates such as crystallized glass in which ⁇ -quartz solid solution is precipitated, quartz glass, metallic silicon, and metal can also be used.
  • the SiO2 - TiO2 -based glass is preferably a quartz glass containing 90-95% by mass of SiO2 and 5-10% by mass of TiO2 .
  • the TiO2 content is 5-10% by mass, the linear expansion coefficient is approximately zero near room temperature, and there is almost no dimensional change near room temperature.
  • the SiO2 - TiO2 -based glass may contain trace components other than SiO2 and TiO2 .
  • the surface of the substrate on which the multilayer reflective film is laminated (hereinafter also referred to as the "first main surface") preferably has high surface smoothness.
  • the surface smoothness of the first main surface can be evaluated by surface roughness.
  • the surface roughness of the first main surface is preferably 0.15 nm or less in terms of root-mean-square roughness Rq.
  • the surface roughness can be measured by an atomic force microscope, and the surface roughness will be described as the root-mean-square roughness Rq based on JIS-B0601:2001.
  • the first main surface is preferably surface-processed to have a predetermined flatness, in order to improve the pattern transfer accuracy and positional accuracy of a reflective mask obtained by using the reflective mask blank.
  • the flatness is preferably 100 nm or less, more preferably 50 nm or less, and even more preferably 30 nm or less.
  • the flatness can be measured by a flatness measuring device manufactured by Fujinon Corporation.
  • the size and thickness of the substrate are appropriately determined based on the design values of the mask, etc.
  • the outer shape is 6 inches (152 mm) square, and the thickness is 0.25 inches (6.3 mm).
  • the substrate preferably has high rigidity in order to prevent deformation due to film stress of films (multilayer reflective film, phase shift film, etc.) formed on the substrate.
  • the Young's modulus of the substrate is preferably 65 GPa or more.
  • the multilayer reflective film of the reflective mask blank of the present invention is not particularly limited as long as it has the desired properties as a reflective film of an EUV mask blank.
  • the multilayer reflective film preferably has a high reflectance to EUV light, and specifically, when EUV light is incident on the surface of the multilayer reflective film at an incident angle of 6°, the maximum reflectance of EUV light at a wavelength of about 13.5 nm is preferably 60% or more, more preferably 65% or more. Similarly, even when a protective film is laminated on the multilayer reflective film, the maximum reflectance of EUV light at a wavelength of about 13.5 nm is preferably 60% or more, more preferably 65% or more.
  • a multilayer reflective film can achieve a high reflectance for EUV light
  • a multilayer reflective film is usually used in which high refractive index layers that exhibit a high refractive index to EUV light and low refractive index layers that exhibit a low refractive index to EUV light are alternately stacked multiple times.
  • the multilayer reflective film may be formed by stacking a high refractive index layer and a low refractive index layer in this order from the substrate side, with one cycle being a laminate structure, and may be formed by stacking a low refractive index layer and a high refractive index layer in this order, with one cycle being a laminate structure, and may be formed by stacking a low refractive index layer and a high refractive index layer in this order, with one cycle being a laminate structure.
  • the high refractive index layer may be a layer containing Si.
  • As the material containing Si in addition to simple Si, a Si compound containing Si and one or more elements selected from the group consisting of B, Be, C, N, and O may be used.
  • the high refractive index layer containing Si By using the high refractive index layer containing Si, a reflective mask having excellent reflectance for EUV light can be obtained.
  • the low refractive index layer a layer containing a metal selected from the group consisting of Mo, Ru, Rh, and Pt, or an alloy thereof can be used.
  • the high refractive index layer is generally made of Si, and the low refractive index layer is generally made of Mo. That is, Mo/Si multilayer reflective film is the most common.
  • the multilayer reflective film is not limited thereto, and Ru/Si multilayer reflective film, Mo/Be multilayer reflective film, Mo compound/Si compound multilayer reflective film, Si/Mo/Ru multilayer reflective film, Si/Mo/Ru/Mo multilayer reflective film, and Si/Ru/Mo/Ru multilayer reflective film can also be used.
  • each layer constituting the multilayer reflective film and the number of repeat units of the layers can be appropriately selected depending on the film material used and the EUV light reflectivity required for the reflective layer.
  • a Mo/Si multilayer reflective film as an example, to create a multilayer reflective film with a maximum EUV light reflectivity of 60% or more, a Mo film with a thickness of 2.3 ⁇ 0.1 nm and a Si film with a thickness of 4.5 ⁇ 0.1 nm can be laminated so that the number of repeat units is 30 to 60.
  • the layers constituting the multilayer reflective film can be formed to the desired thickness using known film formation methods such as magnetron sputtering and ion beam sputtering.
  • ion particles are supplied from an ion source to a target of a high refractive index material and a target of a low refractive index material.
  • the multilayer reflective film is a Mo/Si multilayer reflective film
  • a Si target is used to first form a Si layer of a predetermined thickness on a substrate using ion beam sputtering.
  • a Mo layer of a predetermined thickness is formed using a Mo target. This Si layer and Mo layer constitute one cycle, and 30 to 60 cycles are stacked to form the Mo/Si multilayer reflective film.
  • the layer in contact with the protective film of the multilayer reflective film is preferably made of a material that is resistant to oxidation.
  • the layer made of a material that is resistant to oxidation functions as a cap layer for the multilayer reflective film.
  • the protective film of the reflective mask blank of the present invention is provided for the purpose of protecting the multilayer reflective film from damage caused by an etching process (usually a dry etching process) when a pattern is formed in the absorber film by the etching process.
  • An example of a material that can achieve the above object is a material containing at least one element selected from the group consisting of Ru and Rh. That is, the protective film preferably contains at least one element selected from the group consisting of Ru and Rh.
  • examples of the above-mentioned materials include Rh-based materials such as simple Ru metal, Ru alloys containing Ru and one or more metals selected from the group consisting of Si, Ti, Nb, Rh, and Zr, simple Rh metal, Rh alloys containing Rh and one or more metals selected from the group consisting of Si, Ti, Nb, Ru, Ta, and Zr, Rh-containing nitrides containing the above-mentioned Rh alloys and nitrogen, and Rh-containing oxynitrides containing the above-mentioned Rh alloys, nitrogen, and oxygen.
  • Other examples of materials that can achieve the above object include Al and nitrides containing these metals and nitrogen, and Al 2 O 3 .
  • materials capable of achieving the above object are preferably Ru metal alone, Ru alloys, Rh metal alone, or Rh alloys.
  • As the Ru alloy a Ru-Si alloy is preferred, and as the Rh alloy, a Rh-Si alloy is preferred.
  • the thickness of the protective film is not particularly limited as long as it can function as a protective film.
  • the thickness of the protective film is preferably 1 to 10 nm, more preferably 1.5 to 6 nm, and even more preferably 2 to 5 nm.
  • the material of the protective film is Ru metal alone, a Ru alloy, Rh metal alone, or a Rh alloy, and that the thickness of the protective film is the above-mentioned preferable thickness.
  • the protective film may be a film consisting of a single layer, or may be a multi-layer film consisting of multiple layers.
  • each layer constituting the multi-layer film is preferably made of the above-mentioned preferred materials.
  • the protective film is a multi-layer film, it is also preferable that the total thickness of the multi-layer film is within the above-mentioned preferred range of protective film thickness.
  • the sheet resistance value of the protective film is preferably less than 1.0 ⁇ 10 3 ⁇ /sq., more preferably 7.5 ⁇ 10 2 ⁇ /sq. or less, and even more preferably 5.0 ⁇ 10 2 ⁇ /sq. or less, in order to reduce processing errors when processing with a charged particle beam.
  • There is no particular lower limit to the sheet resistance value of the protective film but examples of the lower limit include 1.0 ⁇ 10 -1 ⁇ /sq. or more, and preferably 1.0 ⁇ 10 0 ⁇ /sq. or more.
  • the sheet resistance can be measured by contacting a measuring terminal with the protective film using a four-point probe method.
  • the sheet resistance can be measured using a surface resistivity meter (Loresta GX MCP-T700, manufactured by Nitto Seiko Analytech Co., Ltd.).
  • the sheet resistance value of the protective film may be measured, for example, by exposing the protective film of the reflective mask blank by a method such as etching.
  • the sheet resistance value of the protective film may be measured by analyzing the components and thickness of the protective film by a known analysis method (for example, transmission scanning electron microscope-energy dispersive X-ray spectroscopy) and preparing a measurement sample for the same components and thickness on another substrate (for example, an insulating substrate), or by preparing a measurement sample on another substrate (for example, an insulating substrate) under the same conditions as those for preparing the protective film.
  • the sheet resistance of the protective film may be measured using a laminate in the middle of the production of a reflective mask blank, that is, for example, a sample having a substrate, a multilayer reflective film, and a protective film formed thereon. The above-mentioned methods yield similar sheet resistance values.
  • the protective film can be formed using known film formation methods such as magnetron sputtering and ion beam sputtering.
  • magnetron sputtering When forming a Ru film using magnetron sputtering, it is preferable to use a Ru target as the target and Ar gas as the sputtering gas.
  • the absorber film of the reflective mask blank of the present invention contains Ru.
  • the absorber film has an O content of 30 atomic % or less based on the total atoms in the absorber film.
  • the absorber film is required to have a high contrast between the EUV light reflected by the multilayer reflective film and the EUV light reflected by the absorber film when the absorber film is patterned.
  • the patterned absorber film (absorber film pattern) may function as a binary mask by absorbing EUV light, or may function as a phase shift mask that reflects EUV light while interfering with the EUV light from the multilayer reflective film to generate contrast.
  • the absorber film may be a single-layer structure consisting of a single layer, or may be a multi-layer structure consisting of two or more layers.
  • the absorber film is preferably a multi-layer structure.
  • the absorber film may also be a film having a so-called anti-reflection function.
  • the layer disposed on the opposite side of the absorber film from the protective film side may be an anti-reflection film when an absorber film pattern inspection is performed using an inspection light (for example, a wavelength of 190 to 320 nm).
  • the O content in the absorber film is 30 atomic % or less, and preferably 20 atomic % or less.
  • the lower limit of the O content is 0 atomic %.
  • the absorber film When the absorber film pattern is used as a binary mask, the absorber film needs to absorb EUV light and have low reflectance for EUV light. Specifically, when the surface of the absorber film is irradiated with EUV light, the maximum reflectance of EUV light at a wavelength of about 13.5 nm is preferably 2% or less.
  • the absorber film preferably contains one or more elements selected from the group consisting of Ta, Ti, Sn, and Cr, and one or more elements selected from the group consisting of C, O, N, B, Hf, and H. Among these, it is preferable to contain at least one element selected from the group consisting of B, C, N, and O, and it is more preferable to contain B or N.
  • the crystal state of the absorber film is easily made into an amorphous or microcrystalline structure.
  • the upper limit and preferred content of O in the absorber film are as described above.
  • the thickness of the absorber film is preferably 40 to 70 nm, and more preferably 50 to 65 nm.
  • the reflectance of the absorber film to EUV light is preferably 2% or more. In order to obtain a sufficient phase shift effect, the reflectance of the absorber film to EUV light is preferably 9 to 15%.
  • the contrast of the optical image on the wafer is improved, and the exposure margin is increased.
  • materials for forming the phase shift mask include materials containing one or more elements selected from the group consisting of Cr, Nb, Ta, Re, Ir, Ag, Os, Au, Pd and Pt.
  • the absorber film preferably includes a first layer that includes Ru and may include a first element selected from the group consisting of Re, Ir, Ag, Os, Au, Pd, and Pt, and a second layer that includes a second element selected from the group consisting of Nb, Ta, and Cr.
  • the first and second layers preferably include at least one element selected from the group consisting of B, C, N, O, and Si, and more preferably include at least one element selected from the group consisting of B, C, N, and O.
  • Examples of materials for forming a phase shift mask include simple substances of the above elements, alloys containing the above elements, oxides of the above elements, nitrides of the above elements, oxynitrides of the above elements, borides of the above elements, silicides (silicides) of the above elements, and carbides of the above elements, as well as composite oxides containing one or more of the above elements, composite nitrides containing one or more of the above elements, composite oxynitrides containing one or more of the above elements, composite borides containing one or more of the above elements, composite silicides containing one or more of the above elements, and composite carbides containing one or more of the above elements.
  • examples of materials for forming a phase shift mask include Ru alone, RuN, RuON, TaN, TaON, Ru alloys containing Ru and one or more metals selected from the group consisting of Cr, Au, Pt, Re, Hf, Ti and Si, TaNb, complex oxides containing Ru and one or more metals or Ta and Nb and O, complex nitrides containing Ru and one or more metals or Ta and Nb and N, complex oxynitrides containing Ru and one or more metals or Ta and Nb and O and N.
  • notations such as "RuON” refer to materials containing Ru, N and O, and the element ratios thereof are not particularly limited as long as the above-mentioned requirements regarding O are satisfied.
  • the upper limit and preferred content of O in the absorber film are as described above. Furthermore, the material of the phase shift mask forming the layer in contact with the protective film is selected to be different from the material forming the protective film.
  • the thickness of the absorber film is preferably from 30 to 60 nm, more preferably from 35 to 55 nm.
  • the types and contents of elements contained in the absorber film are determined by XPS analysis.
  • the analysis of the phase shift film by XPS is performed in the following procedure.
  • an analytical device "PHI 5000 VersaProbe" manufactured by ULVAC-PHI, Inc. is used for the analysis by XPS.
  • the device is calibrated in accordance with JIS K0145.
  • a measurement sample of about 1 cm square is cut out from a reflective mask blank, and the measurement sample is set in a measurement holder so that the phase shift film becomes the measurement surface.
  • a portion of the phase shift film is removed with an argon ion beam, and then measurements are repeatedly performed under the conditions described below.
  • the removed portion is irradiated with X-rays (monochromated AlK ⁇ rays) and analyzed with a photoelectron take-off angle (the angle between the surface of the measurement sample and the direction of the detector) of 45°.
  • X-rays monochromated AlK ⁇ rays
  • a photoelectron take-off angle the angle between the surface of the measurement sample and the direction of the detector
  • a neutralizing gun is used to suppress charge-up.
  • the thickness of the absorber film is determined by X-ray reflectance measurement (XRR, for example, Smart Lab manufactured by RIGAKU Corporation).
  • the crystalline state of the absorber film is preferably amorphous. This increases the smoothness and flatness of the absorber film. Furthermore, increasing the smoothness and flatness of the absorber film reduces the edge roughness of the absorber film pattern, allowing for increased dimensional accuracy of the absorber film pattern.
  • the absorber film can be formed using known film formation methods such as magnetron sputtering and ion beam sputtering.
  • the absorber film when forming a Ru nitride film as the absorber film using magnetron sputtering, the absorber film can be formed by using a Ru target and supplying a gas containing Ar gas and nitrogen gas to perform sputtering.
  • the absorber film can also be formed by using a Ru nitride target and supplying Ar gas to perform sputtering.
  • the outermost layer of the reflective mask blank of the present invention contains at least one element selected from the group consisting of Si, Cr, Nb, Ru, and Ta, and O.
  • the thickness of the outermost layer is less than 4 nm.
  • the outermost layer is located on the surface side of the reflective mask blank opposite to the substrate. It is also preferable that the outermost layer is disposed adjacent to the absorber film.
  • the material constituting the outermost layer is preferably a material containing at least one element selected from the group consisting of Si, Cr, and Ta, and O.
  • the material constituting the outermost layer may further contain at least one element selected from the group consisting of B, C, and N.
  • materials constituting the outermost layer include SiO, SiON, SiOC, CrO, CrON, CrOC, CrOCN, CrBO, NbO, NbON, NbOC, NbOCN, NbBO, RuO, RuON, RuOC, RuOCN, RuBO, TaO, TaON, TaOC, TaOCN, and TaBO, etc.
  • SiON refers to a material containing Si, N, and O, and the element ratios thereof are not particularly limited.
  • the material constituting the outermost layer is selected to be different from the material of the layer adjacent to the outermost layer.
  • the material constituting the outermost layer and the material constituting the absorber film are selected to be different from each other.
  • different materials includes not only embodiments in which the elements contained are different, but also embodiments in which the elements contained are the same but in different ratios.
  • the material constituting the outermost layer is preferably SiO, SiON, CrO, CrON, TaO or TaON, and more preferably SiON, CrON or TaON.
  • the density of the outermost layer is preferably 1.5 to 3.0 g/cm 3 , and more preferably 1.7 to 2.5 g/cm 3 .
  • the density of the outermost layer is preferably 3.5 to 7.0 g/cm 3 , and more preferably 4.5 to 6.0 g/cm 3 .
  • the density of the outermost layer is preferably 6.0 to 15.0 g/cm 3 , and more preferably 6.0 to 12.0 g/cm 3 .
  • the density of each layer is determined by the XRR method.
  • the O content in the outermost layer is preferably 10 atomic % or more, more preferably 20 atomic % or more, and even more preferably 50 atomic % or more.
  • the O content in the outermost layer is preferably 90 atomic % or less, and more preferably 80 atomic % or less.
  • the O content in the outermost layer can be obtained by using angle-resolved XPS or Rutherford backscattering spectrometry.
  • the refractive index n of the outermost layer and the extinction coefficient k of the outermost layer satisfy the following relationship in the wavelength range of 190 to 320 nm: k ⁇ 1.5n-1.5
  • the refractive index n and the extinction coefficient k are determined using ellipsometry (M-2000, manufactured by J. A. Woollam Co.) by performing ellipsometry measurements at an incidence angle of 50 to 75° in the above wavelength range and fitting the obtained data.
  • the outermost layer of the reflective mask blank of the present invention may function as a hard mask film.
  • a hard mask film is formed on the absorber film, dry etching can be performed even if the minimum line width of the absorber film pattern is small, which is effective for miniaturizing the absorber film pattern.
  • the thickness of the outermost layer is less than 4 nm, preferably 3.8 nm or less, and more preferably 2.0 nm or less.
  • the lower limit of the thickness of the outermost layer is 0.1 nm or more, and preferably 0.3 nm or more.
  • the thickness of the outermost layer is obtained in the same manner as the thickness of the absorber film.
  • the outermost layer can be formed by a known film forming method, for example, magnetron sputtering or ion beam sputtering.
  • a reactive sputtering method using a Ta target may be carried out in a gas atmosphere containing a mixture of an inert gas containing at least one of He, Ar, Ne, Kr, and Xe, oxygen gas, and nitrogen gas.
  • the outermost layer may be formed by subjecting a formed layer to an oxidation treatment.
  • the CrON film may be formed by subjecting a formed CrN film to an oxidation treatment.
  • the reflective mask blank of the present invention may have a back surface conductive film on a surface (second main surface) opposite to the first main surface of the substrate.
  • the back surface conductive film preferably has a low sheet resistance value.
  • the sheet resistance value of the back surface conductive film is, for example, preferably 200 ⁇ /sq. or less, and more preferably 100 ⁇ /sq. or less.
  • the material of the back conductive film can be selected from a wide range of materials described in known documents.
  • a high dielectric constant coating described in JP-A-2003-501823 specifically a coating made of Si, Mo, Cr, CrON, or TaSi, can be applied.
  • the material of the back conductive film can be a Cr compound containing Cr and one or more selected from the group consisting of B, N, O, and C, or a Ta compound containing Ta and one or more selected from the group consisting of B, N, O, and C.
  • the thickness of the back surface conductive film is preferably from 10 to 1000 nm, and more preferably from 10 to 400 nm.
  • the back surface conductive film may also have a function of adjusting stress on the second main surface side of the reflective mask blank, i.e., the back surface conductive film can adjust the reflective mask blank to be flat by balancing with stress from various films formed on the first main surface side.
  • the back surface conductive film can be formed by using a known film formation method, for example, a sputtering method such as magnetron sputtering or ion beam sputtering, a CVD method, a vacuum deposition method, or an electrolytic plating method.
  • the interlayer electrical resistance between the surface of the outermost layer opposite to the substrate side and the protective film is preferably 1 to 1000 ⁇ , more preferably 10 to 500 ⁇ , and even more preferably 10 to 100 ⁇ .
  • the interlaminar electrical resistance can be measured by the following method. First, a partial region of the protective film of the reflective mask blank is exposed by a method such as etching. The electrical resistance value between the exposed protective film and the surface of the outermost layer of the reflective mask blank opposite the substrate side is measured using a manual prober (manufactured by Hisol, model: HMP-400).
  • the linear distance in the substrate plane direction between the measurement terminal in contact with the protective film and the measurement terminal in contact with the outermost layer is set to 20 mm.
  • the interlayer electrical resistance between the protective film and the surface of the outermost layer opposite to the substrate side can be measured.
  • the interlayer electrical resistance mainly depends on the electrical resistance of the layer on the opposite side of the protective film from the substrate in the direction perpendicular to the substrate and the thickness of that layer, and the electrical resistance in the horizontal direction of the substrate can be ignored. Therefore, even if the linear distance during the measurement is changed from 20 mm to 100 mm and the interlayer electrical resistance is measured, the value will be the same as when it is 20 mm.
  • the reflective mask can be obtained by patterning the absorber film of the reflective mask blank of the present invention. An example of a method for producing a reflective mask will be described with reference to FIG.
  • FIG. 2A shows a state in which a resist pattern 40 is formed on a reflective mask blank having a substrate 12, a multilayer reflective film 14, a protective film 16, an absorber film 18, and an outermost layer 20 in this order.
  • the resist pattern 40 can be formed by a known method, for example, by applying a resist onto the outermost layer 20 of the reflective mask blank, and then exposing and developing the resist pattern 40.
  • the resist pattern 40 corresponds to a pattern formed on a wafer using a reflective mask. Thereafter, the absorber film 18 and the outermost layer 20 are etched and patterned using the resist pattern 40 in FIG. 2A as a mask, and the resist pattern 40 is removed to obtain a laminate having an absorber film pattern 18pt shown in FIG. 2B.
  • the outermost layer 20 corresponds to a hard mask film
  • the outermost layer 20 located in the opening of the resist pattern 40 may be removed by etching, and the absorber film 18 may be etched and patterned.
  • a resist pattern 41 corresponding to the frame of the exposure region is formed on the laminate of Fig. 2B, and dry etching is performed using the resist pattern 41 of Fig. 2C as a mask. The dry etching is performed until it reaches the substrate 12. After the dry etching, the resist pattern 41 is removed to obtain the reflective mask shown in Fig. 2D.
  • the dry etching used to form the absorber film pattern 18pt may be, for example, dry etching using a Cl-based gas or dry etching using an F-based gas.
  • the etching of the outermost layer 20 disposed in the opening of the resist pattern 40 may be wet etching using a chemical solution or may be dry etching. It is also preferable to select a method for etching the outermost layer 20 by which the outermost layer 20 is etched and the absorber film 18 is not etched.
  • the resist pattern 40 or 41 may be removed by a known method, such as removal with a cleaning solution, such as sulfuric acid-hydrogen peroxide solution (SPM), sulfuric acid, ammonia water, ammonia-hydrogen peroxide solution (APM), OH radical cleaning water, and ozone water.
  • a cleaning solution such as sulfuric acid-hydrogen peroxide solution (SPM), sulfuric acid, ammonia water, ammonia-hydrogen peroxide solution (APM), OH radical cleaning water, and ozone water.
  • the reflective mask obtained by patterning the phase shift film of the reflective mask blank of the present invention can be suitably used as a reflective mask for exposure to EUV light.
  • the reflective mask blank of Example 1 was produced by the following procedure.
  • the substrate used was a SiO 2 -TiO 2 glass substrate (152 mm square, approximately 6.3 mm thick). This glass substrate had 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.
  • the glass substrate was polished so that the surface roughness (root-mean-square roughness Rq) of the main surface was 0.15 nm or less, and the flatness was 100 nm or less.
  • a CrN layer having a thickness of about 100 nm was formed on the back surface of the glass substrate (the surface opposite to the processed surface) by magnetron sputtering to form a back conductive film for an electrostatic chuck.
  • the sheet resistance of the CrN layer was about 100 ⁇ /sq.
  • the glass substrate was fixed in the film-forming chamber by electrostatic attraction using an electrostatic chuck.
  • a multilayer reflective film was formed on the first main surface (the processed surface) of the glass substrate.
  • the reflective multilayer film was formed by ion beam sputtering, in which a Mo layer having a thickness of 2.3 nm and a Si layer having a thickness of 4.5 nm were alternately formed 40 times to form a Mo/Si reflective multilayer film.
  • the Mo layer was formed by ion beam sputtering using a Mo target in an Ar gas atmosphere (gas pressure: 0.02 Pa).
  • the applied voltage was 700 V, and the film formation rate was 3.84 nm/min.
  • the Si layer was formed by using a boron-doped Si target and ion beam sputtering was performed in an Ar gas atmosphere (gas pressure: 0.02 Pa).
  • the applied voltage was 700 V and the film formation rate was 4.62 nm/min.
  • the uppermost layer of the multilayer reflective film was a Si layer.
  • the protective film had a two-layer structure consisting of a Ru layer and a Rh layer in that order from the substrate side.
  • the Ru layer was formed by ion beam sputtering using a Ru target in an Ar gas atmosphere (gas pressure: 0.02 Pa).
  • the applied voltage was 700 V, and the film formation rate was 3.12 nm/min.
  • the thickness of the Ru layer was 1.0 nm.
  • the Rh layer was formed by ion beam sputtering in an Ar gas atmosphere using an Rh target (gas pressure: 0.027 Pa).
  • the applied voltage was 600 V, and the film formation rate was 4.62 nm/min.
  • the thickness of the Rh layer was 1.5 nm.
  • an absorber film was formed on the protective film by ion beam sputtering and magnetron sputtering.
  • the absorber film had a two-layer structure of a RuN layer and a TaN layer in that order from the substrate side.
  • the absorber film was formed in a 148 mm square area with a part of it masked.
  • the RuN layer was formed by magnetron sputtering using a Ru target in an atmosphere of a mixed gas of Ar gas and N2 gas (Ar gas: 80% by volume, N2 gas: 20% by volume) (gas pressure: 0.2 Pa).
  • the input power was 700 W, and the film formation rate was 3.0 nm/min.
  • the thickness of the RuN layer was 29 nm.
  • the TaN layer was formed by magnetron sputtering using a Ta target in an atmosphere of a mixed gas of Ar gas and N2 gas (Ar gas: 95 vol.%, N2 gas: 5 vol.%).
  • the film formation rate was 1.74 nm/min, and the thickness of the TaN layer was 8 nm.
  • a TaON layer which is the outermost layer, was formed by oxygen plasma treatment.
  • the thickness of the outermost layer was 0.6 nm.
  • the outermost layer (TaON layer) formed was composed of TaON, which was formed by oxidizing TaN with oxygen plasma.
  • Example 1 The above procedure was used to obtain the reflective mask blank of Example 1.
  • the sheet resistance values of the conductive layers of the reflective mask blanks of Example 1 and Examples 2 to 7 described below were measured using the above method, and the results are shown in the table below.
  • the reflective mask blank of Example 2 was produced in the same manner as the reflective mask blank of Example 1, except that the outermost layer of TaON was formed under the following conditions.
  • the TaON layer was formed by magnetron sputtering using a Ta target in an atmosphere of a mixed gas of Ar gas, N2 gas, and O2 gas (Ar gas: 60 vol%, N2 gas: 30 vol%, O2 gas: 10 vol%).
  • the film formation rate was 0.6 nm/min, and the thickness of the TaON layer was 3.6 nm.
  • the reflective mask blank of Example 3 was produced in the same manner as the reflective mask blank of Example 1, except that the outermost layer was a SiO layer.
  • the SiO layer was formed by reactive sputtering using a Si target in an atmosphere of a mixed gas of Ar gas and O2 gas (Ar gas: 60% by volume, O2 gas: 40% by volume).
  • the thickness of the SiO layer was 2 nm.
  • the reflective mask blank of Example 4 was produced in the same manner as the reflective mask blank of Example 1, except that the outermost layer was a CrO layer.
  • the CrO layer was formed by reactive sputtering in an atmosphere of a mixed gas of Ar gas and O2 gas (Ar gas: 60% by volume, O2 gas: 40% by volume).
  • the thickness of the CrO layer was 3.2 nm.
  • the reflective mask blank of Example 5 was manufactured in the same manner as the reflective mask blank of Example 1, except that the thickness of the outermost TaON layer was set to 4.3 nm.
  • the reflective mask blank of Example 6 was manufactured in the same manner as the reflective mask blank of Example 1, except that the thickness of the outermost TaON layer was set to 11.5 nm.
  • the reflective mask blank of Example 7 was manufactured in the same manner as the reflective mask blank of Example 1, except that the TaON layer was not formed. Therefore, the TaN layer corresponds to the outermost layer on the side opposite to the substrate.
  • the processing error of the reflective mask blank of each example was evaluated by the following procedure.
  • the reflective mask blank was processed with a charged particle beam to form an evaluation shape using a focused ion beam processing device (Hitachi High-Tech Corporation, model number SMI3050R). Ga was used as the ion species of the ion beam to be irradiated, and the acceleration voltage was 30 kV.
  • the design shape of the evaluation shape was a rectangular parallelepiped shape with a length of 1 ⁇ m, a width of 10 ⁇ m, and a depth of 0.1 ⁇ m.
  • the processing conditions of the focused ion beam processing apparatus were such that the above-mentioned evaluation shape could be accurately formed for the sample in which up to the Ru layer of the protective film was formed in the production of the reflective mask blank of Example 1.
  • an observation sample was prepared by forming a Pt film as an antistatic coating for a scanning electron microscope.
  • the shape of the processed region of the observation sample was observed with a field emission scanning electron microscope (S-4800, manufactured by Hitachi High-Technologies Corporation) from a direction perpendicular to the first main surface of the substrate of the observation sample.
  • the design shape of the evaluation shape was compared with the shape of the machining area to evaluate the machining error.
  • FIG. 3 is a schematic diagram of an observation example when evaluating the processing error of the embodiment.
  • the area shown by the dashed line is a virtual area representing the design shape 30, and the area shown by the solid line is a processing area 32 formed by processing.
  • the protruding portion 34A is an area outside the area of the design shape 30 and inside the area of the processing area 32.
  • the chipped portion 34S is an area inside the area of the design shape 30 and outside the area of the processing area 32.
  • the area S A of the protruding portion is the total area of the protruding portion 34A.
  • the area S S of the chipped portion is the total area of the chipped portion 34S.
  • the evaluation of the processing error was based on the above processing error E (%) and was made according to the following criteria. In practical terms, a rating of A or B is preferable.
  • the inspectability of the reflective mask blank was evaluated by measuring the UV reflectance at a wavelength of 250 nm and based on the following criteria.
  • Table 1 shows the layer structure of each example, and the interlayer electrical resistance, processing error, and evaluation results of inspectability.
  • the thickness of the outermost layer, the ratio of atoms contained in the outermost layer, and the O content in the absorber film shown in Table 1 were obtained by the method described above.
  • the density of the outermost layer shown in Table 1 is the density obtained by XRR.
  • the refractive index n and the extinction coefficient k are values for light of 250 nm determined by the above-mentioned method.
  • the case where the relationship k ⁇ 1.5n ⁇ 1.5 is satisfied is recorded as A, and the case where it is not satisfied is recorded as B.
  • the results of Examples 1 to 4 confirmed that the reflective mask blank of the present invention reduces processing errors when processed with a charged particle beam and also has excellent inspectability.
  • the processing error was large when processing was performed using a charged particle beam.
  • the results of Example 7 it was confirmed that when the outermost layer did not contain O, the inspectability was poor.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Preparing Plates And Mask In Photomechanical Process (AREA)
  • Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)

Abstract

Le but de la présente invention est de fournir une ébauche de masque réfléchissant qui produit peu d'erreurs de traitement lorsqu'elle est soumise à un traitement de rayonnement de particules chargées, et qui présente d'excellentes performances d'inspection.　Une ébauche de masque réfléchissant (10) comporte un substrat (12), un film réfléchissant multicouche (14) qui réfléchit la lumière EUV, un film protecteur (16), un film absorbant (18) et une couche supérieure (20) dans cet ordre. Le film absorbeur (18) comprend du ruthénium, et la teneur en oxygène du film absorbeur (18) est inférieure ou égale à 30 % atomique par rapport à la totalité des atomes du film absorbeur (18). La couche supérieure (20) est située sur le côté le plus à l'extérieur, sur le côté opposé au substrat (12). La couche supérieure (20) comprend de l'oxygène et au moins un élément choisi parmi le silicium, le chrome, le niobium, le ruthénium et le tantale. L'ébauche de masque réfléchissant est conçue de telle sorte que la couche supérieure (20) a une épaisseur de film inférieure à 4 nm.
PCT/JP2023/045963 2023-01-16 2023-12-21 Ébauche de masque réfléchissant, masque réfléchissant et procédé de fabrication de masque réfléchissant Ceased WO2024154535A1 (fr)

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WO2010113700A1 (fr) * 2009-04-02 2010-10-07 凸版印刷株式会社 Masque photographique réfléchissant et plaque-support pour masque photographique réfléchissant
JP2011029334A (ja) * 2009-07-23 2011-02-10 Toshiba Corp 反射型露光用マスクおよび半導体装置の製造方法
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