WO2022255186A1 - Agent chimique, procédé de régénération de substrat avec film, procédé de production de substrat avec film, et procédé de production d'ébauche de masque réfléchissant - Google Patents

Agent chimique, procédé de régénération de substrat avec film, procédé de production de substrat avec film, et procédé de production d'ébauche de masque réfléchissant Download PDF

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Publication number
WO2022255186A1
WO2022255186A1 PCT/JP2022/021397 JP2022021397W WO2022255186A1 WO 2022255186 A1 WO2022255186 A1 WO 2022255186A1 JP 2022021397 W JP2022021397 W JP 2022021397W WO 2022255186 A1 WO2022255186 A1 WO 2022255186A1
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Prior art keywords
film
substrate
multilayer reflective
acid
coated substrate
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PCT/JP2022/021397
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English (en)
Japanese (ja)
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広朗 伊藤
一希 谷津
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Ａｇｃ株式会社
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Priority to JP2023525753A priority Critical patent/JPWO2022255186A1/ja
Publication of WO2022255186A1 publication Critical patent/WO2022255186A1/fr

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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
    • 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
    • G03F1/68—Preparation processes not covered by groups G03F1/20 - G03F1/50
    • G03F1/72—Repair or correction of mask defects
    • 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
    • G03F1/68—Preparation processes not covered by groups G03F1/20 - G03F1/50
    • G03F1/82—Auxiliary processes, e.g. cleaning or inspecting
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
    • H01L21/308—Chemical or electrical treatment, e.g. electrolytic etching using masks

Definitions

  • the present invention relates to a chemical solution, a method for regenerating a substrate with a film, a method for manufacturing a substrate with a film, and a method for manufacturing a reflective mask blank.
  • EUVL Extreme Ultraviolet
  • EUV includes soft X-rays and vacuum ultraviolet rays, and specifically refers to light with a wavelength of approximately 0.2 nm to 100 nm. At present, EUV with a wavelength of about 13.5 nm is mainly considered.
  • a reflective mask is obtained by forming an aperture pattern in an absorbing film of a reflective mask blank.
  • a reflective mask blank includes a substrate such as a glass substrate, a multilayer reflective film formed on the substrate, and an absorbing film formed on the multilayer reflective film.
  • inspections such as surface defect inspections and in-film defect inspections are performed on the film-coated substrate for each process so that unevenness does not exist in the vicinity of the opening pattern. If a defect of unacceptable size is found as a result of the inspection, the defect is removed by cleaning or the like. On the other hand, if there is a defect that cannot be removed by cleaning or the like, at least the multilayer reflective film is peeled off and the substrate is regenerated or discarded as a defective product.
  • Patent Document 1 discloses a method for recycling a substrate with a multilayer film on which a multilayer film having a multilayer reflective film is formed.
  • the substrate with the multilayer film is brought into contact with a chemical solution comprising an aqueous solution containing at least one selected from sodium hydroxide, potassium hydroxide and ammonia, and hydrogen peroxide to peel off the multilayer film from the substrate. to play.
  • Patent Document 1 has the problem that the processing time is long when the film is peeled off from the film-coated substrate, and the substrate damage on the peeled surface is still large.
  • An object of one aspect of the present invention is to shorten the processing time for peeling off a film from a film-coated substrate. Another object of the present invention is to suppress substrate damage on the peeled surface.
  • the present invention is the following [1] to [12].
  • a film-coated substrate having a film having a multilayer reflective film containing silicon and molybdenum on one surface of a glass substrate was treated with a pH adjuster, metaperiodic acid, metaperiodate, and orthoperiodic acid. and at least one oxidizing agent selected from the group consisting of acid, orthoperiodate, permanganic acid, permanganate, and N-methylmorpholine N-oxide, to bring the glass substrate into contact with a chemical solution.
  • a method for reclaiming a film-coated substrate, wherein at least the multilayer reflective film is peeled off from the glass substrate, and the surface of the glass substrate on which the multilayer reflective film was formed is reclaimed.
  • a multilayer reflective film containing at least silicon and molybdenum is formed on one surface of the glass substrate recycled by the method for recycling a film-coated substrate according to any one of [8] to [11].
  • a method of manufacturing a film-coated substrate comprising:
  • [13] Forming a multilayer reflective film containing silicon and molybdenum on one surface of the glass substrate recycled by the method for recycling a film-coated substrate according to any one of [8] to [11]; , forming a protective film containing ruthenium or rhodium on the multilayer reflective film; and selecting from the group consisting of ruthenium, tantalum, chromium, iridium, boron, niobium, rhenium and palladium on the protective film Forming an absorption film containing at least one, and containing at least one selected from the group consisting of chromium, tantalum and boron on the surface of the glass substrate opposite to the surface on which the reflective multilayer film is formed. and forming a conductive film to form a reflective mask blank.
  • FIG. 1 is a flow chart showing a method for manufacturing a reflective mask blank according to one embodiment.
  • FIG. 2 is a cross-sectional view showing an example of a substrate. 3 is a plan view of the substrate of FIG. 2;
  • FIG. 4 is a cross-sectional view showing an example of a reflective mask blank.
  • FIG. 5 is a cross-sectional view showing an example of a reflective mask.
  • FIG. 6 is a diagram showing results of a reference experiment.
  • the method for manufacturing a reflective mask blank has steps S1 to S7.
  • Substrate 2 includes a first major surface 21 and a second major surface 22 facing away from first major surface 21 .
  • the first main surface 21 is rectangular.
  • a rectangular shape includes a shape with chamfered corners. Rectangles also include squares.
  • the second major surface 22 faces away from the first major surface 21 .
  • the second main surface 22 is also rectangular like the first main surface 21 .
  • the substrate 2 also includes four end surfaces 23 , four first chamfered surfaces 24 and four second chamfered surfaces 25 .
  • the end surface 23 is perpendicular to the first major surface 21 and the second major surface 22 .
  • a first chamfered surface 24 is formed at the boundary between the first main surface 21 and the end surface 23 .
  • a second chamfered surface 25 is formed at the boundary between the second main surface 22 and the end surface 23 .
  • the first chamfered surface 24 and the second chamfered surface 25 are so-called C-chamfered surfaces in the present embodiment, they may be R-chamfered surfaces.
  • the substrate 2 is, for example, a glass substrate.
  • the glass of the substrate 2 is preferably silica glass containing titanium oxide (TiO 2 ).
  • Silica glass has a smaller coefficient of linear expansion than general soda-lime glass, and its dimensional change due to temperature change is small.
  • the quartz glass may contain 80% to 95% silicon oxide (SiO 2 ) and 4% to 17% TiO 2 . When the TiO 2 content is 4% to 17%, the linear expansion coefficient is substantially zero near room temperature, and almost no dimensional change occurs near room temperature.
  • Quartz glass may contain third components and impurities other than SiO 2 and TiO 2 . As such quartz glass, for example, Corning's ULE (registered trademark) 7973 series may be used.
  • the size of the substrate 2 in plan view is, for example, 152 mm long and 152 mm wide.
  • the longitudinal and lateral dimensions may be 152 mm or greater.
  • the substrate 2 has a central region 27 and a peripheral region 28 on the first main surface 21 .
  • the central region 27 is a square region of 142 mm long and 142 mm wide, excluding a rectangular frame-shaped peripheral region 28 surrounding the central region 27, and is processed to a desired flatness in steps S1 to S4, This is the quality assurance area.
  • the quality assurance area may have vertical and horizontal dimensions of 142 mm or greater.
  • Four sides of the central region 27 are parallel to the four end faces 23 .
  • the center of central region 27 coincides with the center of first major surface 21 .
  • the second main surface 22 of the substrate 2 also has a central region and a peripheral region, like the first main surface 21 .
  • the central region of the second main surface 22 is a square region of 142 mm long and 142 mm wide, similar to the central region of the first main surface 21, and is processed to a desired flatness by steps S1 to S4 in FIG. It is a quality assurance area.
  • the quality assurance area may have vertical and horizontal dimensions of 142 mm or greater.
  • step S1 the first main surface 21 and the second main surface 22 of the substrate 2 are polished.
  • the first main surface 21 and the second main surface 22 are simultaneously polished by a double-sided polisher (not shown) in this embodiment, but may be polished sequentially by a single-sided polisher (not shown).
  • step S ⁇ b>1 the substrate 2 is polished while supplying polishing slurry between the polishing pad and the substrate 2 .
  • the polishing pad for example, a urethane-based polishing pad, a non-woven fabric-based polishing pad, or a suede-based polishing pad is used.
  • the polishing slurry contains an abrasive and a dispersion medium.
  • the abrasive is, for example, cerium oxide particles.
  • the dispersion medium is, for example, water or an organic solvent.
  • the first main surface 21 and the second main surface 22 may be polished multiple times with abrasives of different materials or grain sizes.
  • the abrasive used in step S1 is not limited to cerium oxide particles.
  • the abrasive used in step S1 may be silicon oxide particles, aluminum oxide particles, zirconium oxide particles, titanium oxide particles, diamond particles, silicon carbide particles, or the like.
  • step S2 the surface shapes of the first main surface 21 and the second main surface 22 of the substrate 2 are measured.
  • a non-contact type measuring instrument such as a laser interference type is used so as not to damage the surface.
  • the measuring machine measures the surface shape of the central region 27 of the first major surface 21 and the central region of the second major surface 22 .
  • step S3 referring to the measurement results in step S2, the first main surface 21 and the second main surface 22 of the substrate 2 are locally processed to improve the flatness.
  • the first main surface 21 and the second main surface 22 are locally machined in order.
  • the order is not particularly limited and may be either one first.
  • the local processing method is, for example, the GCIB (Gas Cluster Ion Beam) method or the PCVM (Plasma Chemical Vaporization Machining) method.
  • the local processing method may be a magnetic fluid polishing method, a rotary polishing tool polishing method, a catalyst-based etching method, or the like. If the flatness after step S1 is sufficient, the local processing in step S3 may be omitted.
  • step S4 finish polishing of the first main surface 21 and the second main surface 22 of the substrate 2 is performed.
  • the first main surface 21 and the second main surface 22 are simultaneously polished by a double-sided polisher (not shown) in this embodiment, but may be polished sequentially by a single-sided polisher (not shown).
  • step S ⁇ b>4 the substrate 2 is polished while supplying polishing slurry between the polishing pad and the substrate 2 .
  • the polishing slurry contains an abrasive.
  • Abrasives are, for example, colloidal silica particles.
  • Conductive film 5 is a metal nitride or metal boride containing at least one element selected from the group consisting of chromium (Cr), tantalum (Ta), titanium (Ti), zirconium (Zr) and niobium (Nb). It is preferably formed with Specific examples of such a conductive film 5 include a CrN film, a TaN film, a TaB film, a CrTaN film, a TiN film and a ZrN film. Conductive film 5 may contain at least one selected from the group consisting of chromium, tantalum and boron.
  • the multilayer reflective film 3 shown in FIG. 4 is formed in the central region of the second main surface 22 of the substrate 2.
  • the multilayer reflective film 3 reflects EUV light.
  • the multilayer reflective film 3 is formed by alternately laminating high refractive index layers and low refractive index layers, for example.
  • the high refractive index layer is made of silicon (Si), for example, and the low refractive index layer is made of molybdenum (Mo), for example.
  • a sputtering method such as an ion beam sputtering method or a magnetron sputtering method is used.
  • the absorbing film 4 shown in FIG. 4 is formed on the multilayer reflective film 3 formed in step S6.
  • the absorption film 4 absorbs EUV.
  • the absorption film 4 is made of a single metal, alloy, nitride, oxide, oxynitride, or the like containing at least one element selected from Ta, Cr, and palladium (Pd), for example.
  • a method for forming the absorbing film 4 for example, an ion beam sputtering method or a sputtering method is used.
  • Absorption film 4 may contain at least one selected from the group consisting of ruthenium, tantalum, chromium, iridium, boron, niobium, rhenium, and palladium.
  • Absorption film 4 may contain at least one selected from the group consisting of ruthenium, tantalum, niobium and boron.
  • steps S6 and S7 are performed after step S5 in this embodiment, they may be performed before step S5.
  • the reflective mask blank 1 shown in FIG. 4 has a first major surface 11 and a second major surface 12 facing away from the first major surface 11, and a light beam extending from the first major surface 11 side to the second major surface 12 side. , a conductive film 5, a substrate 2, a multilayer reflective film 3, and an absorption film 4 in this order.
  • the reflective mask blank 1 has a central region and a peripheral region on the first main surface 11 like the substrate 2 .
  • the central area is a square area of 142 mm long and 142 mm wide, excluding a rectangular frame-shaped peripheral area surrounding the central area, and is a quality assurance area.
  • the reflective mask blank 1 also has a central region and a peripheral region on the second main surface 12 as well as the substrate 2 .
  • the central area is a square area of 142 mm long and 142 mm wide, excluding a rectangular frame-shaped peripheral area surrounding the central area, and is a quality assurance area.
  • the quality assurance area may have vertical and horizontal dimensions of 142 mm or greater.
  • the reflective mask blank 1 may include another film in addition to the conductive film 5, the substrate 2, the multilayer reflective film 3, and the absorbing film 4.
  • the reflective mask blank 1 may further include a protective film.
  • a protective film is formed between the multilayer reflective film 3 and the absorbing film 4 .
  • the protective film protects the multilayer reflective film 3 from being etched when the absorbing film 4 is etched to form the opening pattern 41 in the absorbing film 4 .
  • the protective film is made of, for example, ruthenium (Ru), Si, or TiO2 .
  • the protective film may contain ruthenium or rhodium.
  • a sputtering method is used as a method for forming the protective film.
  • the reflective mask blank 1 may further include a low-reflection film.
  • a low reflection film is formed on the absorption film 4 .
  • an opening pattern 41 is formed in both the low reflection film and the absorption film 4 .
  • the low-reflection film is used for inspection of the opening pattern 41 and has a lower reflection characteristic than the absorption film 4 with respect to inspection light.
  • the low-reflection film is made of, for example, tantalum oxynitride (TaON) or tantalum oxide (TaO).
  • TaON tantalum oxynitride
  • TaO tantalum oxide
  • the reflective mask is obtained by forming an opening pattern 41 in the absorbing film 4.
  • a photolithographic method and an etching method are used to form the opening pattern 41 . Therefore, the reflective mask blank 1 may include the resist film used to form the opening pattern 41 .
  • the film-coated substrate is inspected for surface defects in each process so that unevenness does not exist in the vicinity of the opening pattern 41 .
  • the defect is removed by cleaning.
  • at least the multilayer reflective film 3 is peeled off and the second main surface 22 of the substrate 2 is regenerated or discarded as a defective product.
  • the film-coated substrate means the substrate 2 on which at least the multilayer reflective film 3 is formed, which is obtained after step S6 in FIG.
  • the conductive film 5 may not be formed on the substrate 2 when steps S6 to S7 are performed before step S5. That is, the film-coated substrate includes a substrate 2 on which the multilayer reflective film 3 is formed, a substrate 2 on which the multilayer reflective film 3 and the absorption film 4 are formed, a substrate 2 on which the conductive film 5 and the multilayer reflective film 3 are formed, A substrate 2 (reflective mask blank 1) on which a conductive film 5, a multilayer reflective film 3, and an absorbing film 4 are formed.
  • the film-coated substrate may include other films besides the conductive film 5, the multilayer reflective film 3, and the absorbing film 4, and may include, for example, the protective film and the low-reflection film described above.
  • the film-coated substrate may be a reflective mask with opening patterns 41 formed thereon.
  • the film-coated substrate is brought into contact with a chemical solution in order to peel off at least the multilayer reflective film 3 from the substrate 2 of the film-coated substrate and regenerate the second main surface 22 of the substrate 2 .
  • the film-coated substrate includes another film on the multilayer reflective film 3, that film must also be peeled off at the same time.
  • the film-coated substrate includes the conductive film 5, it is preferable to peel off the conductive film 5 at the same time as the multilayer reflective film 3.
  • the conductive film 5 may be peeled off by another method such as using a chemical solution different from the chemical solution.
  • the method of bringing the film-coated substrate into contact with the chemical solution is not particularly limited, but for example, a method of immersing the film-coated substrate in a chemical solution stored in a treatment tank (hereinafter referred to as an immersion method), or a method of applying the chemical solution to the surface of the film-coated substrate.
  • a spray method is used.
  • the immersion method is more preferable from the viewpoint of productivity and cost.
  • it is easy to repeatedly use the chemical solution. It is preferable to replace the chemical solution whose performance has deteriorated.
  • the processing time is set to be longer than the time (hereinafter referred to as T3 ) required for peeling off the multilayer reflective film 3 from the film-coated substrate 2 .
  • T3 the time required for peeling off the multilayer reflective film 3 from the film-coated substrate 2 .
  • T5 the time required for peeling the conductive film 5
  • the temperature at which the film-coated substrate and the chemical are brought into contact is 20°C to 150°C, preferably 40°C to 100°C. If the temperature is 20° C. or higher, the treatment time can be sufficiently shortened. Also, if the temperature is 150° C. or lower, the substrate 2 is less likely to be excessively damaged by the chemical solution.
  • the recycled substrate 2 is subjected again to at least steps S6 to S7 of FIG. 1 to produce a reflective mask blank 1.
  • steps S1 to S5 may be performed as necessary.
  • the film may be formed after performing local polishing or finish polishing in order to obtain the desired flatness.
  • a chemical solution contains a solvent and an additive.
  • Additives include at least a pH adjuster and an oxidizing agent, and may further include optional additives.
  • Optional additives are, for example, specific metals or chelating agents.
  • the solvent is water or an organic solvent, preferably water. Distilled water, ion-exchanged water, and ultrapure water are preferable as water.
  • the pH adjuster is an organic base or an inorganic base, preferably an inorganic base. If the pH adjuster is an inorganic base, the conductive film 5 can be peeled off when the film-coated substrate has the conductive film 5 containing Ta.
  • Inorganic bases further include, for example, hydroxides of alkali metals or alkaline earth metals. Among these, sodium hydroxide (NaOH), potassium hydroxide (KOH) or rubidium hydroxide (RbOH) is preferable from the viewpoint of basicity and water solubility, NaOH or KOH is more preferable from the viewpoint of cost, and T5 KOH is more preferable because it can be shortened.
  • the concentration of the pH adjuster is adjusted within a range such that the pH of the chemical solution becomes a desired value.
  • the pH of the chemical solution is 10-16, preferably 12-15, more preferably 13-15. If the pH is 10 or more, T3 can be sufficiently shortened when the multilayer reflective film 3 contains Si and Mo. Moreover, if the pH is 16 or less, when the reflective mask blank 1 has a protective film containing Ru, the protective film can be peeled off in a sufficiently short time.
  • the oxidizing agent is included for the purpose of exfoliating at least the multilayer reflective film 3 . Therefore, the oxidizing agent has an oxidation-reduction potential higher than that of at least the components forming the multilayer reflective film 3 .
  • the standard electrode potential of the oxidizing agent is preferably 0.8V to 2.0V . consisting of periodate, orthoperiodic acid (H 5 IO 6 ), orthoperiodate, permanganate (HMnO 4 ), permanganate, and N-methylmorpholine N-oxide (abbreviation: NMO) At least one selected from the group.
  • metaperiodic acid, metaperiodate, orthoperiodic acid, orthoperiodate, permanganic acid, or permanganate is preferable because T3 can be shortened.
  • Metaperiodic acid, metaperiodate, orthoperiodic acid, or orthoperiodate is more preferred because it exhibits high activity even at pH 10 to 16 and the by-product is water-soluble.
  • Permanganic acid or permanganate is also preferable from the point that the conductive film 5 can be peeled off when the film-coated substrate has the conductive film 5 containing Cr.
  • T5 can be shortened when the film-coated substrate has the conductive film 5 containing Ta.
  • the concentration of the oxidizing agent is 0.1 ppm to 40%, preferably 0.1% to 10%, more preferably 0.1% to 2% relative to the chemical solution. If the concentration of the oxidizing agent is 0.1 ppm or more, the multilayer reflective film 3 can be peeled off. In addition, if the concentration of the oxidizing agent is 40% or less, there is little risk of precipitation of sparingly soluble by-products.
  • Optional additives are, for example, specific metals or chelating agents.
  • the specific metals are at least one selected from the group consisting of metals having a higher redox potential than that of Cr(VI) and ions thereof.
  • Specific examples of such metals include Ru and cerium (Ce).
  • the conductive film 5 can be peeled off when the film-coated substrate has the conductive film 5 containing Cr.
  • the Ru ions or Ce ions may be added when the chemical solution is prepared, or may be eluted from a peeled film (for example, a protective film containing Ru).
  • Ru or Ru ions added to the chemical solution are oxidized to Ru(VII) or Ru(VIII) by the oxidizing agent in the chemical solution to become RuO 4 ⁇ or RuO 4 .
  • Ru oxide ions oxidize Cr contained in the conductive film 5 to form water-soluble CrO 4 2 ⁇ , thereby peeling off the conductive film 5 containing Cr.
  • the concentration of the specific metals is 0.0001 to 10 equivalents, preferably 0.001 to 1 equivalent, more preferably 0.01 to 0.1 equivalents relative to the oxidizing agent.
  • concentration of the specific metals is 0.0001 equivalent or more, peeling of the conductive film 5 containing Cr proceeds sufficiently. Also, if the concentration of the specific metals is 10 equivalents or less, substrate damage can be sufficiently suppressed.
  • the chelating agent is an aminocarboxylic acid-based chelating agent, a hydroxy acid-based chelating agent, or a phosphonic acid-based chelating agent.
  • aminocarboxylic acid-based chelating agents include ethylenediaminetetraacetic acid (abbreviation: EDTA), triethylenetetraminehexaacetic acid (abbreviation: TTHA), nitrilotrismethylene phosphonic acid (abbreviation: NTPO) or N,N-bis(2-hydroxy Ethyl)glycine (abbreviation: Bicine) can be mentioned.
  • Hydroxyacid chelating agents include, for example, tartaric acid.
  • phosphonic acid-based chelating agents include hydroxyethylidene diphosphonic acid (abbreviation: HEDP) and phosphonoacetic acid.
  • EDTA or phosphonoacetic acid is more preferable from the viewpoint of shortening the processing time, and TTHA is more preferable from the viewpoint of less damage to the substrate 2 .
  • the concentration of the chelating agent is 0.01% to 10%, preferably 0.1% to 5%, more preferably 0.5% to 2% relative to the drug solution. If the concentration of the chelating agent is 0.01% or more, the treatment time can be significantly shortened. In addition, if the concentration of the chelating agent is 10% or less, there is little risk of precipitation of sparingly soluble by-products.
  • the above additives are mixed with a solvent to prepare a chemical solution. At this time, the additive is selected so that it is soluble in the solvent and does not deposit sparingly soluble by-products.
  • One or more types of each of the pH adjuster and the oxidizing agent are included.
  • the specific metals may not be contained, or one or more kinds may be contained.
  • a chelating agent may be absent or may be included in one or more types.
  • Examples 1 to 23 are examples, and Examples 24 and 25 are comparative examples.
  • Conductive film 5 was formed by sputtering on first main surface 21 of substrate 2 made of quartz glass containing TiO 2 .
  • the conductive film 5 was a CrN film or a film containing Ta as a main component (denoted as Ta-based in Table 1).
  • the multilayer reflective film 3 was formed on the second main surface 22 of the substrate 2 by ion beam sputtering.
  • the multilayer reflective film 3 was formed by alternately laminating Si films of about 4 nm and Mo films of about 3 nm for 40 cycles, and finally laminating Si films of about 4 nm.
  • a protective film made of Ru was formed to a thickness of about 2.5 nm by sputtering. As described above, a film-coated substrate was obtained. A small piece having a side length of about 10 mm was cut out from this film-coated substrate and used as a test piece.
  • this container was placed on a hot plate with a stirrer function and heated for about 30 minutes to keep it at a predetermined temperature. Subsequently, the test piece was put into a container and immersed in the chemical solution for up to 600 minutes while being stirred, and then the test piece was taken out. However, when peeling of all the multilayer reflective film 3 and the conductive film 5 was confirmed, the test piece was taken out at that time. Detachment of the multilayer reflective film 3 or the conductive film 5 was visually confirmed before taking out the test piece, and after taking out the test piece, the film components were determined using a fluorescent X-ray analysis (manufactured by Rigaku: ZSX Primus II). I checked again to make sure it wasn't there. Incidentally, when the multilayer reflective film 3 was peeled off, the protective film was also peeled off at the same time.
  • a fluorescent X-ray analysis manufactured by Rigaku: ZSX Primus II
  • NaOH NaOH was used in Example 1
  • KOH was used in Examples 2 to 25 at a predetermined concentration.
  • RuCl 3 was added in Examples 6 and 7, and Ru powder was added in Example 8 in a predetermined equivalent amount to the oxidizing agent.
  • Example 9 As a chelating agent, 0.1% of EDTA was added in Example 9, TTHA in Example 10, NTPO in Example 11, Bicine in Example 12, tartaric acid in Example 13, and phosphonoacetic acid in Example 14, respectively.
  • the pH of the chemical solutions of Examples 1 to 25 was measured using a portable pH/ORP/ion meter (manufactured by Horiba Advanced Techno Co., Ltd.: D-73).
  • T3 can be shortened by using KOH as a pH adjuster than by using NaOH.
  • Example 3 From the comparison between Example 3 and Examples 6 to 8, when Ru or Ru ions are added as specific metals, not only the multilayer reflective film 3 but also the conductive film 5 made of CrN can be peeled off while suppressing damage to the substrate. It became clear.
  • Example 2 A comparison of Example 2 with Examples 9-14 reveals that the addition of a chelating agent can shorten T3 .
  • Example 24 when the oxidizing agent was H 2 O 2 as in Example 24, the multilayer reflective film 3 could not be peeled off even after 600 minutes. Further, as in Example 25, when the chelating agent was added to the chemical solution of Example 24, the multilayer reflective film 3 could be peeled off, but the time required for peeling was longer than in Examples 1 to 22. In addition, Example 23 was equivalent to Example 25 in T3 , but was superior in terms of substrate damage.
  • a multilayer reflective film 3 was formed by a sputtering method on the second main surface 22 of the substrate 2 made of quartz glass containing TiO 2 .
  • the multilayer reflective film 3 was formed by alternately laminating Si films of about 4 nm and Mo films of about 3 nm for 40 cycles, and finally laminating Si films of about 4 nm.
  • a protective film made of Ru was formed to a thickness of about 2.5 nm by sputtering. As described above, a film-coated substrate was obtained.
  • reaction vessel filled with 1 L (liter) of chemical solution using 22.4% KOH as a pH adjuster and 1% NaIO 4 as an oxidizing agent was kept at 60-65°C, and then the reaction vessel was The film-coated substrate was added while stirring. When peeling of the multilayer reflective film 3 was visually confirmed, the film-coated substrate was taken out, and another film-coated substrate prepared in the same manner was newly introduced. This was repeated 8 times in succession.
  • FIG. 6 shows the results of the above reference experiment. As shown in FIG. 1, T3 tended to increase slightly as the number of film-coated substrates increased, but the change was not such that the chemical solution had to be replaced. This suggests that the chemical solution according to the present invention can be sufficiently repeatedly used.
  • REFERENCE SIGNS LIST 1 reflective mask blank 2 substrate 3 multilayer reflective film 4 absorbing film 5 conductive film 41 aperture pattern

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Abstract

Un agent chimique selon un mode de réalisation de la présente invention contient un agent de réglage du pH et au moins un oxydant qui est choisi dans le groupe constitué par l'acide méthacrylique, un sel de métapériodate, un acide orthopériodique, un sel d'orthopériodate, de l'acide sulfurique, un sel de permanganate et un N-oxyde de N-méthylmorpholine.
PCT/JP2022/021397 2021-06-04 2022-05-25 Agent chimique, procédé de régénération de substrat avec film, procédé de production de substrat avec film, et procédé de production d'ébauche de masque réfléchissant WO2022255186A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007189174A (ja) * 2006-01-16 2007-07-26 Nikon Corp 多層膜反射鏡、その再生方法および露光装置
JP2011127221A (ja) * 2009-11-18 2011-06-30 Hoya Corp 基板の再生方法、マスクブランクの製造方法、多層反射膜付き基板の製造方法、及び反射型マスクブランクの製造方法
JP2013174012A (ja) * 2012-02-02 2013-09-05 Sematech Inc 堆積システムのシールド表面のコーティング
JP2017181733A (ja) * 2016-03-30 2017-10-05 Hoya株式会社 多層膜付き基板の再生方法、多層反射膜付き基板の製造方法、及び反射型マスクブランクの製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007189174A (ja) * 2006-01-16 2007-07-26 Nikon Corp 多層膜反射鏡、その再生方法および露光装置
JP2011127221A (ja) * 2009-11-18 2011-06-30 Hoya Corp 基板の再生方法、マスクブランクの製造方法、多層反射膜付き基板の製造方法、及び反射型マスクブランクの製造方法
JP2013174012A (ja) * 2012-02-02 2013-09-05 Sematech Inc 堆積システムのシールド表面のコーティング
JP2017181733A (ja) * 2016-03-30 2017-10-05 Hoya株式会社 多層膜付き基板の再生方法、多層反射膜付き基板の製造方法、及び反射型マスクブランクの製造方法

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