WO2022255186A1 - Chemicall agent, method for regenerating substrate with film, method for producing substrate with film, and method for producing reflective mask blank - Google Patents
Chemicall agent, method for regenerating substrate with film, method for producing substrate with film, and method for producing reflective mask blank Download PDFInfo
- 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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- WIPO (PCT)
- Prior art keywords
- film
- substrate
- multilayer reflective
- acid
- coated substrate
- Prior art date
Links
- 239000000758 substrate Substances 0.000 title claims description 139
- 238000000034 method Methods 0.000 title claims description 50
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 230000001172 regenerating effect Effects 0.000 title claims description 7
- 239000003795 chemical substances by application Substances 0.000 title claims 2
- 239000007800 oxidant agent Substances 0.000 claims abstract description 26
- 239000003002 pH adjusting agent Substances 0.000 claims abstract description 15
- TWLXDPFBEPBAQB-UHFFFAOYSA-N orthoperiodic acid Chemical compound OI(O)(O)(O)(O)=O TWLXDPFBEPBAQB-UHFFFAOYSA-N 0.000 claims abstract description 11
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 9
- KHIWWQKSHDUIBK-UHFFFAOYSA-M periodate Chemical class [O-]I(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-M 0.000 claims abstract description 9
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims description 51
- 239000002738 chelating agent Substances 0.000 claims description 26
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000011521 glass Substances 0.000 claims description 21
- 230000001681 protective effect Effects 0.000 claims description 21
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- 239000011651 chromium Substances 0.000 claims description 17
- 229910052707 ruthenium Inorganic materials 0.000 claims description 16
- 150000002739 metals Chemical class 0.000 claims description 15
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 15
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 14
- 229910052715 tantalum Inorganic materials 0.000 claims description 14
- 229910052710 silicon Inorganic materials 0.000 claims description 12
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 11
- 229910052796 boron Inorganic materials 0.000 claims description 11
- 229910052750 molybdenum Inorganic materials 0.000 claims description 11
- 229910052804 chromium Inorganic materials 0.000 claims description 10
- 239000010703 silicon Substances 0.000 claims description 10
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 9
- 150000002500 ions Chemical class 0.000 claims description 9
- 239000011733 molybdenum Substances 0.000 claims description 9
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 9
- 239000010955 niobium Substances 0.000 claims description 8
- 238000004064 recycling Methods 0.000 claims description 8
- 229910052758 niobium Inorganic materials 0.000 claims description 7
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 4
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 4
- 239000003814 drug Substances 0.000 claims description 4
- 229940079593 drug Drugs 0.000 claims description 4
- 150000001261 hydroxy acids Chemical class 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 3
- 238000011069 regeneration method Methods 0.000 claims description 3
- 229910052702 rhenium Inorganic materials 0.000 claims description 3
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 239000010948 rhodium Substances 0.000 claims description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 230000008929 regeneration Effects 0.000 claims 1
- 150000003839 salts Chemical class 0.000 abstract 2
- 239000013043 chemical agent Substances 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 45
- 238000005498 polishing Methods 0.000 description 16
- 230000007547 defect Effects 0.000 description 14
- 238000010521 absorption reaction Methods 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 239000002245 particle Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 238000004544 sputter deposition Methods 0.000 description 8
- 239000000654 additive Substances 0.000 description 7
- 238000007689 inspection Methods 0.000 description 7
- 230000002093 peripheral effect Effects 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 238000000275 quality assurance Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- XUYJLQHKOGNDPB-UHFFFAOYSA-N phosphonoacetic acid Chemical compound OC(=O)CP(O)(O)=O XUYJLQHKOGNDPB-UHFFFAOYSA-N 0.000 description 6
- 229910010413 TiO 2 Inorganic materials 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 238000010030 laminating Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 150000007529 inorganic bases Chemical class 0.000 description 4
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- RAEOEMDZDMCHJA-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-[2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]ethyl]amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CCN(CC(O)=O)CC(O)=O)CC(O)=O RAEOEMDZDMCHJA-UHFFFAOYSA-N 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- FSVCELGFZIQNCK-UHFFFAOYSA-N N,N-bis(2-hydroxyethyl)glycine Chemical compound OCCN(CCO)CC(O)=O FSVCELGFZIQNCK-UHFFFAOYSA-N 0.000 description 3
- 238000001900 extreme ultraviolet lithography Methods 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 238000001659 ion-beam spectroscopy Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 241000872931 Myoporum sandwicense Species 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- 239000003082 abrasive agent Substances 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000007998 bicine buffer Substances 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- JQWHASGSAFIOCM-UHFFFAOYSA-M sodium periodate Chemical compound [Na+].[O-]I(=O)(=O)=O JQWHASGSAFIOCM-UHFFFAOYSA-M 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- 239000011975 tartaric acid Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- BAERPNBPLZWCES-UHFFFAOYSA-N (2-hydroxy-1-phosphonoethyl)phosphonic acid Chemical compound OCC(P(O)(O)=O)P(O)(O)=O BAERPNBPLZWCES-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000012217 deletion Methods 0.000 description 1
- 230000037430 deletion Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 239000011553 magnetic fluid Substances 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- -1 nitrilotrismethylene phosphonic acid Chemical compound 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 150000007530 organic bases Chemical group 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- JMOHEPRYPIIZQU-UHFFFAOYSA-N oxygen(2-);tantalum(2+) Chemical compound [O-2].[Ta+2] JMOHEPRYPIIZQU-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
Classifications
-
- 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
A chemical agent according to one embodiment of the present invention contains a pH adjusting agent and at least one oxidant that is selected from the group consisting of metaperiodic acid, a metaperiodate salt, orthoperiodic acid, an orthoperiodate salt, permanganic acid, a permanganate salt and N-methylmorpholine N-oxide.
Description
本発明は、薬液、膜付き基板の再生方法、膜付き基板の製造方法、および反射型マスクブランクの製造方法に関する。
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.
近年、半導体デバイスの微細化に伴い、極端紫外線（Ｅｘｔｒｅｍｅ Ｕｌｔｒａ－Ｖｉｏｌｅｔ：ＥＵＶ）を用いた露光技術であるＥＵＶリソグラフィー（ＥＵＶＬ）が開発されている。ＥＵＶとは、軟Ｘ線および真空紫外線を含み、具体的には波長が０．２ｎｍ～１００ｎｍ程度の光のことである。現時点では、１３．５ｎｍ程度の波長のＥＵＶが主に検討されている。
In recent years, with the miniaturization of semiconductor devices, EUV lithography (EUVL), which is an exposure technology using Extreme Ultraviolet (EUV), has been developed. 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.
ＥＵＶＬでは、反射型マスクの開口パターンを半導体基板に転写する。反射型マスクは、反射型マスクブランクの吸収膜に開口パターンを形成することで得られる。反射型マスクブランクは、ガラス基板などの基板と、基板の上に形成される多層反射膜と、多層反射膜の上に形成される吸収膜と、を含む。
In EUVL, the opening pattern of the reflective mask is transferred to the semiconductor substrate. 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.
ところで、反射型マスクにおいて、開口パターンの近傍に凹凸が存在すると、転写されるパターンの位置精度やコントラストが悪化し問題となる。凹凸は、傷や異物などの欠陥により生じる。
By the way, in a reflective mask, if unevenness exists in the vicinity of the opening pattern, the positional accuracy and contrast of the pattern to be transferred deteriorate, resulting in a problem. The unevenness is caused by defects such as scratches and foreign matter.
従って、開口パターンの近傍に凹凸が存在することのないよう、膜付き基板に対し、工程ごとに表面欠陥検査や膜中欠陥検査などの検査を実施する。検査の結果、許容できないサイズの欠陥が発見されたときは、洗浄等により欠陥を除去する。一方で、洗浄等によっても除去できない欠陥がある場合は、少なくとも多層反射膜を剥離して基板を再生するか、または不良品として破棄する。
Therefore, 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.
特許文献１には、多層反射膜を有する多層膜が基板上に形成された多層膜付き基板の再生方法が開示されている。この再生方法では、水酸化ナトリウム、水酸化カリウムおよびアンモニアから選択される少なくとも１つと過酸化水素とを含む水溶液からなる薬液に、多層膜付基板を接触させて基板から多層膜を剥離し、基板を再生する。
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. In this regeneration method, 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.
しかしながら、特許文献１に記載の方法では、膜付き基板の基板から膜を剥離する際の処理時間が長く、また、剥離された面の基板ダメージが依然として大きいという問題があった。
However, the method described in 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.
本発明の一態様は、膜付き基板の基板から膜を剥離する際の処理時間を短縮することを目的とする。また、剥離された面の基板ダメージを抑制することを目的とする。
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.
本発明は、以下の［１］～［１２］である。
The present invention is the following [1] to [12].
［１］ ガラス基板の一方の面にケイ素およびモリブデンを含有する多層反射膜を有する膜が形成された膜付き基板の前記ガラス基板から、少なくとも前記多層反射膜を剥離するために用いられる薬液であって、ｐＨ調整剤と、メタ過ヨウ素酸、メタ過ヨウ素酸塩、オルト過ヨウ素酸、オルト過ヨウ素酸塩、過マンガン酸、過マンガン酸塩、およびＮ－メチルモルホリンＮ－オキシドからなる群から選択される少なくとも１つの酸化剤と、を含む、薬液。
[1] A chemical solution used for peeling at least the multilayer reflective film from the glass substrate of the film-coated substrate having a film having a multilayer reflective film containing silicon and molybdenum formed on one surface of the glass substrate. and a pH adjusting agent from the group consisting of metaperiodic acid, metaperiodate, orthoperiodic acid, orthoperiodate, permanganate, permanganate, and N-methylmorpholine N-oxide and at least one selected oxidizing agent.
［２］ ｐＨが１０以上１６以下である、［１］に記載の薬液。
[2] The chemical solution according to [1], which has a pH of 10 or more and 16 or less.
［３］ 前記ｐＨ調整剤は、水酸化ナトリウムまたは水酸化カリウムである、［１］に記載の薬液。
[3] The chemical solution according to [1], wherein the pH adjuster is sodium hydroxide or potassium hydroxide.
［４］ 前記酸化剤は、メタ過ヨウ素酸、メタ過ヨウ素酸塩、オルト過ヨウ素酸またはオルト過ヨウ素酸塩である、［１］に記載の薬液。
[4] The chemical solution according to [1], wherein the oxidizing agent is metaperiodic acid, metaperiodate, orthoperiodic acid, or orthoperiodate.
［５］ 前記酸化剤は、過マンガン酸または過マンガン酸塩である、［１］に記載の薬液。
[5] The chemical solution according to [1], wherein the oxidizing agent is permanganic acid or permanganate.
［６］ クロム（ＶＩ）の酸化還元電位よりも高い酸化還元電位を有する金属およびそのイオンからなる群から選択される少なくとも１つを、前記酸化剤に対して０．０００１モル当量～１０モル当量さらに含む、［１］に記載の薬液。
[6] Adding at least one selected from the group consisting of metals having a redox potential higher than that of chromium (VI) and ions thereof in an amount of 0.0001 to 10 molar equivalents relative to the oxidizing agent The chemical solution according to [1], further comprising:
［７］ キレート剤としてアミノカルボン酸系キレート剤、ヒドロキシ酸系キレート剤またはホスホン酸系キレート剤をさらに含む、［１］に記載の薬液。
[7] The drug solution according to [1], further comprising an aminocarboxylic acid-based chelating agent, a hydroxy acid-based chelating agent, or a phosphonic acid-based chelating agent as a chelating agent.
［８］ ガラス基板の一方の面にケイ素およびモリブデンを含有する多層反射膜を有する膜が形成された膜付き基板を、ｐＨ調整剤と、メタ過ヨウ素酸、メタ過ヨウ素酸塩、オルト過ヨウ素酸、オルト過ヨウ素酸塩、過マンガン酸、過マンガン酸塩、およびＮ－メチルモルホリンＮ－オキシドからなる群から選択される少なくとも１つの酸化剤と、を含む薬液に接触させて、前記ガラス基板から少なくとも前記多層反射膜を剥離し、前記ガラス基板の前記多層反射膜が形成されていた面を再生することを特徴とする、膜付き基板の再生方法。
[8] 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.
［９］ 前記膜付き基板は、前記多層反射膜の上に、ルテニウムを含有する保護膜を有する、［８］に記載の膜付き基板の再生方法。
[9] The method for recycling a film-coated substrate according to [8], wherein the film-coated substrate has a protective film containing ruthenium on the multilayer reflective film.
［１０］ 前記膜付き基板は、前記多層反射膜の上に、ルテニウム、タンタル、ニオブおよびホウ素からなる群から選択される少なくとも１つを含有する吸収膜を有する、［８］に記載の膜付き基板の再生方法。
[10] The film-coated substrate according to [8], wherein the film-coated substrate has an absorption film containing at least one selected from the group consisting of ruthenium, tantalum, niobium and boron on the multilayer reflective film. Substrate regeneration method.
［１１］ 前記膜付き基板は、前記多層反射膜が形成された面とは反対の面に、クロムまたはタンタルを含有する導電膜を有する、［８］に記載の膜付き基板の再生方法。
[11] The method for recycling a film-coated substrate according to [8], wherein the film-coated substrate has a conductive film containing chromium or tantalum on the surface opposite to the surface on which the multilayer reflective film is formed.
［１２］ ［８］～［１１］のいずれか１つに記載の膜付き基板の再生方法により再生された前記ガラス基板の一方の面に、少なくとも、ケイ素およびモリブデンを含有する多層反射膜を形成することを含む、膜付き基板の製造方法。
[12] 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］ ［８］～［１１］のいずれか１つに記載の膜付き基板の再生方法により再生された前記ガラス基板の一方の面にケイ素およびモリブデンを含有する多層反射膜を形成することと、前記多層反射膜の上にルテニウムまたはロジウムを含有する保護膜を形成することと、前記保護膜の上にルテニウム、タンタル、クロム、イリジウム、ホウ素、ニオブ、レニウムおよびパラジウムからなる群から選択される少なくとも１つを含有する吸収膜を形成することと、前記ガラス基板の前記反射多層膜が形成された面とは反対の面にクロム、タンタルおよびホウ素からなる群から選択される少なくとも１つを含有する導電膜を形成することと、を含む、反射型マスクブランクの製造方法。
[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.
以下、本発明の実施するための形態（以下、単に本実施形態という。）について、図面を参照して説明する。図面中、上下左右等の位置関係は、特に断らない限り、図面に示す位置関係に基づくものとする。なお、図面の寸法比率は図示の比率に限られるものではない。また、明細書中、数値範囲を示す「～」は、その前後に記載された数値を下限値及び上限値として含むことを意味する。前記下限値及び前記上限値は、四捨五入の範囲を含む。さらに、「％」、「ｐｐｍ」および「ｐｐｂ」は、質量分率を表すものとし、「当量」はモル当量を表すものとする。
Hereinafter, a mode for carrying out the present invention (hereinafter simply referred to as this embodiment) will be described with reference to the drawings. In the drawings, the positional relationships such as top, bottom, left, and right are based on the positional relationships shown in the drawings unless otherwise specified. Note that the dimensional ratios in the drawings are not limited to the illustrated ratios. In the specification, "-" indicating a numerical range means that the numerical values before and after it are included as lower and upper limits. The lower limit value and the upper limit value include the rounding range. Furthermore, "%", "ppm" and "ppb" shall denote mass fractions and "equivalents" shall denote molar equivalents.
（反射型マスクブランクの製造方法）
図１に示すように、反射型マスクブランクの製造方法は、ステップＳ１～Ｓ７を有する。反射型マスクブランクの製造には、例えば図２及び図３に示す基板２を用いる。基板２は、第１主表面２１と、第１主表面２１とは反対向きの第２主表面２２とを含む。第１主表面２１は、矩形状である。本明細書において、矩形状とは、角に面取加工を施した形状を含む。また、矩形は、正方形を含む。第２主表面２２は、第１主表面２１とは反対向きである。第２主表面２２も、第１主表面２１と同様に、矩形状である。 (Manufacturing method of reflective mask blank)
As shown in FIG. 1, the method for manufacturing a reflective mask blank has steps S1 to S7. Asubstrate 2 shown in FIGS. 2 and 3, for example, is used for manufacturing a reflective mask blank. 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. In this specification, 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 .
図１に示すように、反射型マスクブランクの製造方法は、ステップＳ１～Ｓ７を有する。反射型マスクブランクの製造には、例えば図２及び図３に示す基板２を用いる。基板２は、第１主表面２１と、第１主表面２１とは反対向きの第２主表面２２とを含む。第１主表面２１は、矩形状である。本明細書において、矩形状とは、角に面取加工を施した形状を含む。また、矩形は、正方形を含む。第２主表面２２は、第１主表面２１とは反対向きである。第２主表面２２も、第１主表面２１と同様に、矩形状である。 (Manufacturing method of reflective mask blank)
As shown in FIG. 1, the method for manufacturing a reflective mask blank has steps S1 to S7. A
また、基板２は、４つの端面２３と、４つの第１面取面２４と、４つの第２面取面２５とを含む。端面２３は、第１主表面２１及び第２主表面２２に対して垂直である。第１面取面２４は、第１主表面２１と端面２３の境界に形成される。第２面取面２５は、第２主表面２２と端面２３の境界に形成される。第１面取面２４及び第２面取面２５は、本実施形態では、いわゆるＣ面取面であるが、Ｒ面取面であってもよい。
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 . Although 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.
基板２は、例えばガラス基板である。基板２のガラスは、酸化チタン（ＴｉＯ２）を含有する石英ガラスが好ましい。石英ガラスは、一般的なソーダライムガラスに比べて、線膨張係数が小さく、温度変化による寸法変化が小さい。石英ガラスは、酸化ケイ素（ＳｉＯ２）を８０％～９５％、ＴｉＯ２を４％～１７％含んでよい。ＴｉＯ２含有量が４％～１７％であると、室温付近での線膨張係数が略ゼロであり、室温付近での寸法変化がほとんど生じない。石英ガラスは、ＳｉＯ２およびＴｉＯ２以外の第三成分や不純物を含んでもよい。このような石英ガラスとして、例えば、Ｃｏｒｎｉｎｇ社のＵＬＥ（登録商標）７９７３シリーズを用いてもよい。
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.
平面視にて基板２のサイズは、例えば縦１５２ｍｍ、横１５２ｍｍである。縦寸法及び横寸法は、１５２ｍｍ以上であってもよい。
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.
基板２は、第１主表面２１に中央領域２７と周縁領域２８とを有する。中央領域２７は、その中央領域２７を取り囲む矩形枠状の周縁領域２８を除く、縦１４２ｍｍ、横１４２ｍｍの正方形の領域であり、ステップＳ１～Ｓ４によって所望の平坦度に加工される領域であり、品質保証領域である。品質保証領域は、縦寸法及び横寸法が１４２ｍｍ以上であってもよい。中央領域２７の４つの辺は、４つの端面２３に平行である。中央領域２７の中心は、第１主表面２１の中心に一致する。
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 .
なお、図示しないが、基板２の第２主表面２２も、第１主表面２１と同様に、中央領域と、周縁領域とを有する。第２主表面２２の中央領域は、第１主表面２１の中央領域と同様に、縦１４２ｍｍ、横１４２ｍｍの正方形の領域であって、図１のステップＳ１～Ｓ４によって所望の平坦度に加工される領域であり、品質保証領域である。品質保証領域は、縦寸法及び横寸法が１４２ｍｍ以上であってもよい。
Although not shown, 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.
まず、ステップＳ１では、基板２の第１主表面２１及び第２主表面２２を研磨する。第１主表面２１及び第２主表面２２は、本実施形態では不図示の両面研磨機で同時に研磨されるが、不図示の片面研磨機で順番に研磨されてもよい。ステップＳ１では、研磨パッドと基板２の間に研磨スラリーを供給しながら、基板２を研磨する。
First, in 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). In step S<b>1 , the substrate 2 is polished while supplying polishing slurry between the polishing pad and the substrate 2 .
研磨パッドとしては、例えばウレタン系研磨パッド、不織布系研磨パッド、またはスウェード系研磨パッドなどが用いられる。研磨スラリーは、研磨剤と分散媒とを含む。研磨剤は、例えば酸化セリウム粒子である。分散媒は、例えば水または有機溶剤である。第１主表面２１及び第２主表面２２は、異なる材質または粒度の研磨剤で、複数回研磨されてもよい。
As 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.
なお、ステップＳ１で用いられる研磨剤は、酸化セリウム粒子には限定されない。例えば、ステップＳ１で用いられる研磨剤は、酸化シリコン粒子、酸化アルミニウム粒子、酸化ジルコニウム粒子、酸化チタン粒子、ダイヤモンド粒子、または炭化珪素粒子などであってもよい。
The abrasive used in step S1 is not limited to cerium oxide particles. For example, 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.
次に、ステップＳ２では、基板２の第１主表面２１及び第２主表面２２の表面形状を測定する。表面形状の測定には、例えば、表面が傷付かないように、レーザー干渉式などの非接触式の測定機が用いられる。測定機は、第１主表面２１の中央領域２７、及び第２主表面２２の中央領域の表面形状を測定する。
Next, in step S2, the surface shapes of the first main surface 21 and the second main surface 22 of the substrate 2 are measured. For surface shape measurement, for example, 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 .
次に、ステップＳ３では、ステップＳ２の測定結果を参照し、平坦度を向上すべく、基板２の第１主表面２１および第２主表面２２を局所加工する。第１主表面２１と第２主表面２２は、順番に局所加工される。その順番は、どちらが先でもよく、特に限定されない。局所加工の方法は、例えばＧＣＩＢ（Ｇａｓ Ｃｌｕｓｔｅｒ Ｉｏｎ Ｂｅａｍ）法、またはＰＣＶＭ（Ｐｌａｓｍａ Ｃｈｅｍｉｃａｌ Ｖａｐｏｒｉｚａｔｉｏｎ Ｍａｃｈｉｎｉｎｇ）法である。局所加工の方法は、磁性流体による研磨法、回転研磨ツールによる研磨法、または触媒基準エッチング法等であってもよい。なお、ステップＳ１後の平坦度が十分であれば、ステップＳ３の局所加工はしなくてもよい。
Next, in 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.
次に、ステップＳ４では、基板２の第１主表面２１及び第２主表面２２の仕上げ研磨を行う。第１主表面２１及び第２主表面２２は、本実施形態では不図示の両面研磨機で同時に研磨されるが、不図示の片面研磨機で順番に研磨されてもよい。ステップＳ４では、研磨パッドと基板２の間に研磨スラリーを供給しながら、基板２を研磨する。研磨スラリーは、研磨剤を含む。研磨剤は、例えばコロイダルシリカ粒子である。
Next, in 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). In 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.
次に、ステップＳ５では、基板２の第１主表面２１の中央領域２７に、図４に示す導電膜５を形成する。導電膜５は、反射型マスクを露光装置の静電チャックに吸着するのに用いられる。導電膜５は、クロム（Ｃｒ），タンタル（Ｔａ），チタン（Ｔｉ），ジルコニウム（Ｚｒ）およびニオブ（Ｎｂ）からなる群より選ばれた１種以上の元素を含む金属窒化物または金属ホウ化物で形成されることが好ましい。このような導電膜５の具体例としては、ＣｒＮ膜、ＴａＮ膜、ＴａＢ膜、ＣｒＴａＮ膜、ＴｉＮ膜およびＺｒＮ膜が例示される。導電膜５は、クロム、タンタルおよびホウ素からなる群から選択される少なくとも１つを含有してもよい。
Next, in step S5, the conductive film 5 shown in FIG. 4 is formed in the central region 27 of the first main surface 21 of the substrate 2. The conductive film 5 is used to attract the reflective mask to the electrostatic chuck of the exposure apparatus. 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.
次に、ステップＳ６では、基板２の第２主表面２２の中央領域に、図４に示す多層反射膜３を形成する。多層反射膜３は、ＥＵＶ光を反射する。多層反射膜３は、例えば高屈折率層と低屈折率層とを交互に積層したものである。高屈折率層は例えばケイ素（Ｓｉ）で形成され、低屈折率層は例えばモリブデン（Ｍｏ）で形成される。多層反射膜３の成膜方法としては、例えばイオンビームスパッタリング法、マグネトロンスパッタリング法などのスパッタリング法が用いられる。
Next, in step S6, 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. As a method for forming the multilayer reflective film 3, for example, a sputtering method such as an ion beam sputtering method or a magnetron sputtering method is used.
最後に、ステップＳ７では、ステップＳ６で形成された多層反射膜３の上に、図４に示す吸収膜４を形成する。吸収膜４は、ＥＵＶを吸収する。吸収膜４は、例えばＴａ、Ｃｒ、パラジウム（Ｐｄ）から選ばれる少なくとも１つの元素を含む単金属、合金、窒化物、酸化物、酸窒化物などで形成される。吸収膜４の成膜方法としては、例えばイオンビームスパッタリング法、スパッタリング法が用いられる。吸収膜４は、ルテニウム、タンタル、クロム、イリジウム、ホウ素、ニオブ、レニウム、およびパラジウムからなる群から選択される少なくとも１つを含有してもよい。吸収膜４は、ルテニウム、タンタル、ニオブおよびホウ素からなる群から選択される少なくとも１つを含有してもよい。
Finally, in step S7, 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. As 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.
なお、ステップＳ６～Ｓ７は、本実施形態ではステップＳ５の後に実施されるが、ステップＳ５の前に実施されてもよい。
Although steps S6 and S7 are performed after step S5 in this embodiment, they may be performed before step S5.
上記ステップＳ１～Ｓ７により、図４に示す反射型マスクブランク１が得られる。反射型マスクブランク１は、第１主表面１１と、第１主表面１１とは反対向きの第２主表面１２とを有し、第１主表面１１の側から第２主表面１２の側に、導電膜５と、基板２と、多層反射膜３と、吸収膜４とをこの順番で有する。
Through the above steps S1 to S7, the reflective mask blank 1 shown in FIG. 4 is obtained. The reflective mask blank 1 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.
反射型マスクブランク１は、図示しないが、基板２と同様に、第１主表面１１に中央領域と周縁領域とを有する。中央領域は、その中央領域を取り囲む矩形枠状の周縁領域を除く、縦１４２ｍｍ、横１４２ｍｍの正方形の領域であり、品質保証領域である。また、反射型マスクブランク１は、基板２と同様に、第２主表面１２にも中央領域と周縁領域とを有する。中央領域は、その中央領域を取り囲む矩形枠状の周縁領域を除く、縦１４２ｍｍ、横１４２ｍｍの正方形の領域であり、品質保証領域である。品質保証領域は、縦寸法及び横寸法が１４２ｍｍ以上であってもよい。
Although not shown, 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.
なお、反射型マスクブランク１は、導電膜５と、基板２と、多層反射膜３と、吸収膜４とに加えて、別の膜を含んでもよい。
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.
例えば、反射型マスクブランク１は、更に、保護膜を含んでもよい。保護膜は、多層反射膜３と吸収膜４との間に形成される。保護膜は、吸収膜４に開口パターン４１を形成すべく吸収膜４をエッチングする際に、多層反射膜３がエッチングされないように、多層反射膜３を保護する。保護膜は、例えばルテニウム（Ｒｕ）、Ｓｉ、またはＴｉＯ２などで形成される。保護膜は、ルテニウムまたはロジウムを含有してもよい。保護膜の成膜方法としては、例えばスパッタリング法が用いられる。
For example, 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. As a method for forming the protective film, for example, a sputtering method is used.
また、反射型マスクブランク１は、更に、低反射膜を含んでもよい。低反射膜は、吸収膜４上に形成される。その後、低反射膜と吸収膜４の両方に、開口パターン４１が形成される。低反射膜は、開口パターン４１の検査に用いられ、検査光に対して吸収膜４よりも低反射特性を有する。低反射膜は、例えば酸窒化タンタル（ＴａＯＮ）または酸化タンタル（ＴａＯ）などで形成される。低反射膜の成膜方法としては、例えばスパッタリング法が用いられる。
In addition, the reflective mask blank 1 may further include a low-reflection film. A low reflection film is formed on the absorption film 4 . After that, 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). As a method for forming the low-reflection film, for example, a sputtering method is used.
図５に示すように、反射型マスクは、吸収膜４に開口パターン４１を形成して得られる。開口パターン４１の形成には、フォトリソグラフィ法およびエッチング法が用いられる。従って、開口パターン４１の形成に用いられるレジスト膜が、反射型マスクブランク１に含まれてもよい。
As shown in FIG. 5, the reflective mask is obtained by forming an opening pattern 41 in the absorbing film 4. As shown in FIG. 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 .
（膜付き基板の再生方法）
ところで、反射型マスクにおいて、開口パターン４１の近傍に凹凸が存在すると、転写されるパターンの位置精度やコントラストが悪化し問題となる。凹凸は、傷や異物などの欠陥により生じる。 (Method for Regenerating Film-Coated Substrate)
By the way, in the reflective mask, if unevenness exists in the vicinity of theopening pattern 41, the positional accuracy and contrast of the pattern to be transferred deteriorate, resulting in a problem. The unevenness is caused by defects such as scratches and foreign matter.
ところで、反射型マスクにおいて、開口パターン４１の近傍に凹凸が存在すると、転写されるパターンの位置精度やコントラストが悪化し問題となる。凹凸は、傷や異物などの欠陥により生じる。 (Method for Regenerating Film-Coated Substrate)
By the way, in the reflective mask, if unevenness exists in the vicinity of the
従って、開口パターン４１の近傍に凹凸が存在することのないよう、膜付き基板に対し、工程ごとに表面欠陥検査を実施する。表面欠陥検査の結果、許容できないサイズの欠陥が発見されたときは、洗浄により欠陥を除去する。一方で、洗浄によっても除去できない欠陥がある場合は、少なくとも多層反射膜３を剥離して、基板２の第２主表面２２を再生するか、または不良品として破棄する。
Therefore, 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 . As a result of the surface defect inspection, if a defect of an unacceptable size is found, the defect is removed by cleaning. On the other hand, if there is a defect that cannot be removed even 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.
ここで、膜付き基板とは、図１のステップＳ６以降に得られる、少なくとも多層反射膜３が形成された基板２を意味する。なお、ステップＳ６～Ｓ７がステップＳ５の前に実施される場合は、基板２に導電膜５が形成されていなくてもよい。すなわち、膜付き基板は、多層反射膜３が形成された基板２、多層反射膜３と吸収膜４とが形成された基板２、導電膜５と多層反射膜３とが形成された基板２、導電膜５と多層反射膜３と吸収膜４とが形成された基板２（反射型マスクブランク１）などである。また、膜付き基板は、導電膜５、多層反射膜３および吸収膜４以外にも別の膜を含んでもよく、例えば、上述した保護膜や低反射膜を含んでもよい。さらに、膜付き基板は、開口パターン４１が形成された反射型マスクであってもよい。
Here, 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. Note that 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. In addition, 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. Furthermore, the film-coated substrate may be a reflective mask with opening patterns 41 formed thereon.
本実施形態では、膜付き基板の基板２から少なくとも多層反射膜３を剥離して、基板２の第２主表面２２を再生するために、膜付き基板を薬液と接触させる。このとき、膜付き基板が多層反射膜３の上に他の膜を含む場合は、その膜をも同時に剥離する必要がある。また、膜付き基板が導電膜５を含む場合は、多層反射膜３と同時に導電膜５をも剥離することが好ましいが、同時に導電膜５をも剥離することができないときは、本発明に係る薬液とは異なる薬液を用いる等、別の方法によって導電膜５を剥離してもよい。
In this embodiment, 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 . At this time, if the film-coated substrate includes another film on the multilayer reflective film 3, that film must also be peeled off at the same time. When 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.
膜付き基板を薬液と接触させる方法としては、特に限定されないが、例えば処理槽に溜めた薬液に膜付き基板を浸漬する方法（以下、浸漬法という。）、または膜付き基板の表面に薬液を噴き付ける方法が用いられる。これらの方法のうち、浸漬法は、生産性やコストの観点からより好ましい。浸漬法の場合は、薬液を繰り返し使用することが容易である。性能が低下した薬液は、交換されることが好ましい。
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. Among these methods, the immersion method is more preferable from the viewpoint of productivity and cost. In the case of the immersion method, it is easy to repeatedly use the chemical solution. It is preferable to replace the chemical solution whose performance has deteriorated.
膜付き基板と薬液を接触させる際の処理時間は、生産性の観点から、短ければ短いほど好ましい。処理時間は、膜付き基板の基板２から多層反射膜３を剥離するのに要する時間（以下、Ｔ３という。）よりも長く設定される。薬液によって多層反射膜３と同時に導電膜５をも剥離することができる場合は、処理時間は、Ｔ３および導電膜５を剥離するのに要する時間（以下、Ｔ５という。）のうちいずれか長い方よりも長く設定される。Ｔ３およびＴ５はいずれも、短ければ短いほど、処理時間が短くなるので好ましい。
From the viewpoint of productivity, the shorter the processing time when the film-coated substrate is brought into contact with the chemical solution, the better. 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 . When the conductive film 5 can be peeled off at the same time as the multilayer reflective film 3 by the chemical solution, the processing time is either T3 or the time required for peeling the conductive film 5 (hereinafter referred to as T5 ). It is set longer than the longer one. For both T3 and T5 , the shorter the better, the shorter the treatment time.
膜付き基板と薬液を接触させる際の温度は、２０℃～１５０℃であり、４０℃～１００℃が好ましい。温度が２０℃以上であれば、処理時間を十分に短くすることができる。また、温度が１５０℃以下であれば、薬液により基板２が過度にダメージを受ける恐れが少ない。
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.
再生された基板２は、少なくとも図１のステップＳ６～Ｓ７に再び供され、反射型マスクブランク１が製造される。このとき、基板２の状態により、必要に応じてステップＳ１～Ｓ５を実施してもよい。例えば、全ての膜が剥離された基板２において、平坦度が十分でない場合は、所望の平坦度とするために、局所研磨や仕上げ研磨を実施した後に、膜を形成してもよい。
The recycled substrate 2 is subjected again to at least steps S6 to S7 of FIG. 1 to produce a reflective mask blank 1. At this time, depending on the state of the substrate 2, steps S1 to S5 may be performed as necessary. For example, if the flatness of the substrate 2 from which all the films have been removed is not sufficient, the film may be formed after performing local polishing or finish polishing in order to obtain the desired flatness.
また、以上のように基板２を再生して反射型マスクブランク１を製造したときに、洗浄によっても除去できない欠陥が再度発生した場合は、そのような欠陥が発生しなくなるまで、以上の操作を繰り返し行ってもよい。
Further, when the substrate 2 is recycled to manufacture the reflective mask blank 1 as described above, if a defect that cannot be removed by cleaning occurs again, the above operations are repeated until such a defect no longer occurs. You can repeat.
（薬液）
続いて、本実施形態に係る薬液について、詳細に説明する。 (Chemical solution)
Next, the chemical solution according to this embodiment will be described in detail.
続いて、本実施形態に係る薬液について、詳細に説明する。 (Chemical solution)
Next, the chemical solution according to this embodiment will be described in detail.
薬液は、溶媒と添加剤とを含む。添加剤は、少なくともｐＨ調整剤および酸化剤を含み、さらに任意添加物を含んでもよい。任意添加物とは、例えば特定金属類またはキレート剤である。
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.
溶媒は、水または有機溶媒であり、水が好ましい。水としては、蒸留水、イオン交換水、超純水が好ましい。
The solvent is water or an organic solvent, preferably water. Distilled water, ion-exchanged water, and ultrapure water are preferable as water.
ｐＨ調整剤は、有機塩基または無機塩基であり、無機塩基が好ましい。ｐＨ調整剤が無機塩基であれば、膜付き基板がＴａを含む導電膜５を有する場合に導電膜５を剥離することができる。さらに、無機塩基としては、例えば、アルカリ金属またはアルカリ土類金属の水酸化物が挙げられる。これらの中でも、塩基性度および水溶性の観点から水酸化ナトリウム（ＮａＯＨ）、水酸化カリウム（ＫＯＨ）または水酸化ルビジウム（ＲｂＯＨ）が好ましく、コストの観点からＮａＯＨまたはＫＯＨがより好ましく、Ｔ５を短縮することができる点からＫＯＨがさらに好ましい。
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.
ｐＨ調整剤の濃度は、薬液のｐＨが所望の値となるような範囲に調整される。薬液のｐＨは、１０～１６であり、１２～１５が好ましく、１３～１５がより好ましい。ｐＨが１０以上であれば、多層反射膜３がＳｉおよびＭｏを含む場合に、Ｔ３を十分に短くすることができる。また、ｐＨが１６以下であれば、反射型マスクブランク１がＲｕを含む保護膜を有する場合に、保護膜を十分に短い時間で剥離することができる。
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.
酸化剤は、少なくとも多層反射膜３を剥離する目的で含まれる。従って、酸化剤は、少なくとも多層反射膜３を構成する成分の酸化還元電位よりも高い酸化還元電位を有する。例えば、多層反射膜３がＳｉおよびＭｏを含むときは、酸化剤の標準電極電位が０．８Ｖ～２．０Ｖであることが好ましく、具体的には、メタ過ヨウ素酸（ＨＩＯ４）、メタ過ヨウ素酸塩、オルト過ヨウ素酸（Ｈ５ＩＯ６）、オルト過ヨウ素酸塩、過マンガン酸（ＨＭｎＯ４）、過マンガン酸塩、およびＮ－メチルモルホリンＮ－オキシド（略：ＮＭＯ）からなる群から選択される少なくとも１つである。
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 . For example, when the multilayer reflective film 3 contains Si and Mo, 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.
上記の酸化剤の中でも、Ｔ３を短縮することができる点からメタ過ヨウ素酸、メタ過ヨウ素酸塩、オルト過ヨウ素酸、オルト過ヨウ素酸塩、過マンガン酸または過マンガン酸塩が好ましく、ｐＨ１０～１６においても高い活性を示し、かつ副生成物が水溶性であることから、メタ過ヨウ素酸、メタ過ヨウ素酸塩、オルト過ヨウ素酸またはオルト過ヨウ素酸塩がより好ましい。また、膜付き基板がＣｒを含む導電膜５を有する場合には導電膜５を剥離できる点から、過マンガン酸または過マンガン酸塩も好ましい。
Among the above oxidizing agents, 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.
また、薬液が酸化剤を含むとき、膜付き基板がＴａを含む導電膜５を有する場合にＴ５を短縮することができる。
Further, when the chemical solution contains an oxidizing agent, T5 can be shortened when the film-coated substrate has the conductive film 5 containing Ta.
酸化剤の濃度は、薬液に対して０．１ｐｐｍ～４０％であり、好ましくは０．１％～１０％であり、より好ましくは０．１％～２％である。酸化剤の濃度が０．１ｐｐｍ以上であれば、多層反射膜３を剥離することができる。また、酸化剤の濃度が４０％以下であれば、難溶性の副生成物が析出する恐れが小さい。
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.
任意添加物は、例えば特定金属類またはキレート剤である。
Optional additives are, for example, specific metals or chelating agents.
特定金属類とは、Ｃｒ（ＶＩ）の酸化還元電位よりも高い酸化還元電位を有する金属およびそのイオンからなる群から選択される少なくとも１つである。このような金属の具体例としては、Ｒｕまたはセリウム（Ｃｅ）が挙げられる。薬液が特定金属類を含むとき、膜付き基板がＣｒを含む導電膜５を有する場合に導電膜５を剥離できる。なお、ＲｕイオンまたはＣｅイオンは、薬液を調製する際に加えられてもよく、剥離された膜（例えば、Ｒｕを含む保護膜）から溶出したものであってもよい。
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). When the chemical solution contains specific metals, the conductive film 5 can be peeled off when the film-coated substrate has the conductive film 5 containing Cr. Note that 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).
以下に、特定金属類により、Ｃｒを含む導電膜５が剥離されるメカニズムを、Ｒｕを例にして説明する。薬液中に添加されたＲｕまたはＲｕイオンは、薬液中の酸化剤によりＲｕ（ＶＩＩ）またはＲｕ（ＶＩＩＩ）まで酸化され、ＲｕＯ４
－またはＲｕＯ４の状態となる。これらのＲｕ酸化物イオンが、導電膜５に含まれるＣｒを酸化し、水溶性のＣｒＯ４
２－とすることで、Ｃｒを含む導電膜５が剥離される。
The mechanism by which the conductive film 5 containing Cr is peeled off by specific metals will be described below using Ru as an example. 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 . These 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.
特定金属類の濃度は、酸化剤に対して０．０００１当量～１０当量であり、好ましくは０．００１当量～１当量であり、より好ましくは０．０１当量～０．１当量である。特定金属類の濃度が０．０００１当量以上であれば、Ｃｒを含む導電膜５の剥離が十分に進行する。また、特定金属類の濃度が１０当量以下であれば、基板ダメージを十分に抑制することができる。
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. When the 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.
キレート剤は、アミノカルボン酸系キレート剤、ヒドロキシ酸系キレート剤またはホスホン酸系キレート剤である。アミノカルボン酸系キレート剤としては、例えばエチレンジアミン四酢酸（略：ＥＤＴＡ）、トリエチレンテトラミン六酢酸（略：ＴＴＨＡ）、ニトリロトリスメチレンホスホン酸（略：ＮＴＰＯ）またはＮ，Ｎ－ビス（２－ヒドロキシエチル）グリシン（略：Ｂｉｃｉｎｅ）が挙げられる。ヒドロキシ酸キレート剤は、例えば酒石酸が挙げられる。ホスホン酸系キレート剤としては、例えばヒドロキシエチリデンジホスホン酸（略：ＨＥＤＰ）またはホスホノ酢酸が挙げられる。薬液が上記のキレート剤を含むとき、処理時間を短縮することができる。
The chelating agent is an aminocarboxylic acid-based chelating agent, a hydroxy acid-based chelating agent, or a phosphonic acid-based chelating agent. Examples of 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. Examples of phosphonic acid-based chelating agents include hydroxyethylidene diphosphonic acid (abbreviation: HEDP) and phosphonoacetic acid. When the chemical solution contains the chelating agent, the treatment time can be shortened.
上記のキレート剤の中でも、処理時間がより短縮される点からＥＤＴＡまたはホスホノ酢酸が、基板２へのダメージの少なさの観点からＴＴＨＡが、より好ましい。
Among the above chelating agents, 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 .
キレート剤の濃度は、薬液に対して０．０１％～１０％であり、好ましくは０．１％～５％であり、より好ましくは０．５％～２％である。キレート剤の濃度が０．０１％以上であれば、処理時間を有意に短縮することができる。また、キレート剤の濃度が１０％以下であれば、難溶性の副生成物が析出する恐れが小さい。
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.
以上の添加剤を溶媒と混合し、薬液を調製する。このとき、添加剤は、溶媒に溶け、かつ難溶性の副生成物が析出しないように選択される。ｐＨ調整剤および酸化剤は、それぞれ１種類以上含まれる。特定金属類は、含まれなくてもよく、１種類以上含まれてもよい。キレート剤は、含まれなくてもよく、１種類以上含まれてもよい。
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.
次に、表１を参照して、実験データについて説明する。なお、表１において、例１～２３は実施例であり、例２４および２５は比較例である。
Next, the experimental data will be described with reference to Table 1. In Table 1, Examples 1 to 23 are examples, and Examples 24 and 25 are comparative examples.
ＴｉＯ２を含有する石英ガラスからなる基板２の第１主表面２１に、スパッタリング法により導電膜５を形成した。導電膜５は、ＣｒＮ膜またはＴａを主成分とする膜（表１中、Ｔａ系と表記する。）であった。続いて、基板２の第２主表面２２に、イオンビームスパッタリング法により多層反射膜３を形成した。多層反射膜３は、約４ｎｍのＳｉ膜と約３ｎｍのＭｏ膜とを交互に４０周期積層した後、最後に約４ｎｍのＳｉ膜を積層したものであった。続いて、多層反射膜３の上に、スパッタリング法によりＲｕからなる保護膜を約２．５ｎｍ形成した。以上により、膜付き基板を得た。この膜付き基板から、１辺の長さが約１０ｍｍの小片を切り出し、試験片とした。
次に、薬液を調製し、容器に満たした後、この容器をスターラー機能付きホットプレートに設置し、約３０分間加熱して所定の温度に保たれるようにした。続いて、容器に試験片を投入し、薬液を攪拌しながら最大で６００分浸漬し、その後試験片を取り出した。ただし、多層反射膜３および導電膜５の全ての剥離が確認された場合は、その時点で試験片を取り出した。多層反射膜３または導電膜５の剥離は、試験片を取り出す前は目視にて確認し、試験片を取り出した後にも、蛍光Ｘ線分析（リガク社製：ＺＳＸ ＰｒｉｍｕｓＩＩ）を用いて膜成分が残存していないことを再度確認した。なお、多層反射膜３が剥離されたときは、保護膜も同時に剥離されていた。
Next, after preparing the chemical solution and filling it in a container, 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.
（薬液）
溶媒として、超純水を用いた。 (Chemical solution)
Ultrapure water was used as a solvent.
溶媒として、超純水を用いた。 (Chemical solution)
Ultrapure water was used as a solvent.
ｐＨ調整剤として、例１ではＮａＯＨを、例２～２５ではＫＯＨをそれぞれ所定の濃度として用いた。
As a pH adjuster, NaOH was used in Example 1, and KOH was used in Examples 2 to 25 at a predetermined concentration.
酸化剤として、例１～１４、１８および１９ではメタ過ヨウ素酸ナトリウム（ＮａＩＯ４）を、例１５～１７および２０ではＨ５ＩＯ６を、例２１および２２では過マンガン酸カリウム（ＫＭｎＯ４）を、例２３ではＮＭＯを、例２４および２５では過酸化水素（Ｈ２Ｏ２）をそれぞれ所定の濃度として用いた。
As the oxidizing agent, sodium metaperiodate (NaIO 4 ) in Examples 1-14, 18 and 19, H 5 IO 6 in Examples 15-17 and 20, and potassium permanganate (KMnO 4 ) in Examples 21 and 22. , NMO in Example 23, and hydrogen peroxide (H 2 O 2 ) in Examples 24 and 25, respectively, at given concentrations.
特定金属類として、例６および７ではＲｕＣｌ３を、例８ではＲｕ粉末を、それぞれ酸化剤に対して所定の当量だけ添加した。
As specific metals, 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.
キレート剤として、例９ではＥＤＴＡを、例１０ではＴＴＨＡを、例１１ではＮＴＰＯを、例１２ではＢｉｃｉｎｅを、例１３では酒石酸を、例１４ではホスホノ酢酸をそれぞれ０．１％添加した。
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.
なお、例１～２５の薬液のｐＨは、ポータブル型ｐＨ・ＯＲＰ・イオンメータ（堀場アドバンストテクノ社製：Ｄ－７３）を用いて測定した。
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).
（実験結果）
表１中、容器に試験片を投入してから多層反射膜３の剥離を目視で確認するまでの時間（Ｔ３）が３０分以内のときを「Ａ」、３０分超４５分以下のときを「Ｂ」、４５分超６０分以下のときを「Ｃ」、６０分超１２０分以下のときを「Ｄ」、１２０分超６００分未満のときを「Ｅ」とし、また、６００分時点で剥離していなかったときを「×」と表すこととする。なお、多層反射膜３が剥離されたときは、保護膜も同時に剥離されていたので、保護膜の剥離に要した時間は評価していない。 (Experimental result)
In Table 1, "A" indicates that the time (T 3 ) from placing the test piece in the container to visually confirming peeling of the multilayerreflective film 3 is within 30 minutes, and "A" is more than 30 minutes and 45 minutes or less. "B" when more than 45 minutes and 60 minutes or less, "C" when more than 60 minutes and 120 minutes or less, "E" when more than 120 minutes and less than 600 minutes, and at 600 minutes When there was no peeling in , it is represented as "x". When the multilayer reflective film 3 was peeled off, the protective film was also peeled off at the same time, so the time required for peeling off the protective film was not evaluated.
表１中、容器に試験片を投入してから多層反射膜３の剥離を目視で確認するまでの時間（Ｔ３）が３０分以内のときを「Ａ」、３０分超４５分以下のときを「Ｂ」、４５分超６０分以下のときを「Ｃ」、６０分超１２０分以下のときを「Ｄ」、１２０分超６００分未満のときを「Ｅ」とし、また、６００分時点で剥離していなかったときを「×」と表すこととする。なお、多層反射膜３が剥離されたときは、保護膜も同時に剥離されていたので、保護膜の剥離に要した時間は評価していない。 (Experimental result)
In Table 1, "A" indicates that the time (T 3 ) from placing the test piece in the container to visually confirming peeling of the multilayer
表１中、容器に試験片を投入してから導電膜５の剥離を目視で確認するまでの時間（Ｔ５）については、Ｔ３と同様に評価した。
In Table 1, the time (T 5 ) from when the test piece was put into the container until the peeling of the conductive film 5 was visually confirmed was evaluated in the same manner as T 3 .
また、表１中、原子間力顕微鏡（Ｂｒｕｋｅｒ社製：Ｄｉｍｅｎｓｉｏｎ Ｉｃｏｎ）によって測定した、基板２の第２主表面２２の二乗平均粗さ（ＲＭＳ）が実験後に０．１５ｎｍ以下であったときを「◎」、０．１５ｎｍ超０．５ｎｍ以下であったときを「○」と表すことで、基板ダメージを評価した。ＲＭＳが０．５ｎｍ以下であれば、基板２を再生した後に再研磨する際の工程負荷を十分に軽減することができる。
Also, in Table 1, when the root-mean-square roughness (RMS) of the second main surface 22 of the substrate 2 measured by an atomic force microscope (manufactured by Bruker: Dimension Icon) was 0.15 nm or less after the experiment. Substrate damage was evaluated by expressing “⊚” and “◯” when the thickness was more than 0.15 nm and 0.5 nm or less. If the RMS is 0.5 nm or less, it is possible to sufficiently reduce the process load when the substrate 2 is re-polished after being recycled.
例１～２３の結果が示すように、本発明に係る薬液により、少なくとも多層反射膜３を剥離することができた。
As shown by the results of Examples 1 to 23, at least the multilayer reflective film 3 could be peeled off with the chemical solution according to the present invention.
例１および例２より、ｐＨ調整剤としてＫＯＨを用いた方が、ＮａＯＨの場合よりもＴ３を短縮できることが明らかとなった。
From Examples 1 and 2, it became clear that T3 can be shortened by using KOH as a pH adjuster than by using NaOH.
例３と例６～８との比較より、特定金属類としてＲｕまたはＲｕイオンを添加すると、基板ダメージを抑制したまま、多層反射膜３に加えて、ＣｒＮからなる導電膜５をも剥離できることが明らかとなった。
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.
例２と例９～例１４との比較により、キレート剤を添加すると、Ｔ３を短縮できることが明らかとなった。
A comparison of Example 2 with Examples 9-14 reveals that the addition of a chelating agent can shorten T3 .
一方で、例２４のように、酸化剤がＨ２Ｏ２であるときは、６００分経過しても多層反射膜３を剥離することができなかった。また、例２５のように、例２４の薬液にキレート剤を加えると多層反射膜３を剥離することができたものの、例１～例２２に比較して剥離に要した時間が長かった。また、例２３は、例２５と比較してＴ３は同等であったが、基板ダメージの点で優れていた。
On the other hand, 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.
また、ルテニウム系、タンタル系、ニオブ系またはホウ素系の吸収膜を成膜したＳｉウエハの試験片についても上記実験方法にて膜の剥離を試みたところ、これらの吸収膜についても剥離できることが明らかとなった。ガラス基板上の多層反射膜の最上層はケイ素を含有する膜であるため、この結果から、ガラス基板上に形成された多層反射膜上の、ルテニウム系、タンタル系、ニオブ系またはホウ素系の吸収膜も剥離できることがわかった。
In addition, when an attempt was made to remove the film from a Si wafer test piece with a ruthenium-, tantalum-, niobium-, or boron-based absorbing film by the above-described experimental method, it was found that these absorbing films could also be peeled off. became. Since the top layer of the multilayer reflective film on the glass substrate is a silicon-containing film, this result suggests that the ruthenium-, tantalum-, niobium-, or boron-based absorption on the multilayer reflective film formed on the glass substrate. It was found that the film can also be peeled off.
（参考実験）
ＴｉＯ２を含有する石英ガラスからなる基板２の第２主表面２２に、スパッタリング法により多層反射膜３を形成した。多層反射膜３は、約４ｎｍのＳｉ膜と約３ｎｍのＭｏ膜とを交互に４０周期積層した後、最後に約４ｎｍのＳｉ膜を積層したものであった。続いて、多層反射膜３の上に、スパッタリング法によりＲｕからなる保護膜を約２．５ｎｍ形成した。以上により、膜付き基板を得た。 (reference experiment)
A multilayerreflective 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. Subsequently, on the multilayer reflective film 3, 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.
ＴｉＯ２を含有する石英ガラスからなる基板２の第２主表面２２に、スパッタリング法により多層反射膜３を形成した。多層反射膜３は、約４ｎｍのＳｉ膜と約３ｎｍのＭｏ膜とを交互に４０周期積層した後、最後に約４ｎｍのＳｉ膜を積層したものであった。続いて、多層反射膜３の上に、スパッタリング法によりＲｕからなる保護膜を約２．５ｎｍ形成した。以上により、膜付き基板を得た。 (reference experiment)
A multilayer
次に、ｐＨ調整剤として２２．４％のＫＯＨ、酸化剤として１％のＮａＩＯ４を用いた薬液１Ｌ（リットル）で満たされた反応槽を、６０～６５℃に保った後、反応槽を攪拌させながら上記の膜付き基板を投入した。多層反射膜３の剥離を目視で確認した時点で膜付き基板を取り出し、同様に作製した別の膜付き基板を新たに投入した。これを連続で８回行った。
Next, the 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.
以上の参考実験の結果を図６に示す。図１より、膜付き基板の投入回数が増えるほど、Ｔ３はわずかに増加する傾向が見られたが、薬液を交換しなければいけないほどの変化ではなかった。このことから、本発明に係る薬液は、十分に繰り返し使用できることが示唆された。
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.
以上、本発明に係る薬液、膜付き基板の再生方法、膜付き基板の製造方法、および反射型マスクブランクの製造方法について説明したが、本発明は上記実施形態などに限定されない。特許請求の範囲に記載された範疇内において、各種の変更、修正、置換、付加、削除、及び組み合わせが可能である。それらについても当然に本開示の技術的範囲に属する。
The chemical solution, the method for regenerating a substrate with a film, the method for manufacturing a substrate with a film, and the method for manufacturing a reflective mask blank according to the present invention have been described above, but the present invention is not limited to the above embodiments. Various changes, modifications, substitutions, additions, deletions, and combinations are possible within the scope of the claims. These also naturally belong to the technical scope of the present disclosure.
本出願は、２０２１年６月４日に日本国特許庁に出願した特願２０２１－０９４７２４号に基づく優先権を主張するものであり、特願２０２１－０９４７２４号の全内容を本出願に援用する。
This application claims priority based on Japanese Patent Application No. 2021-094724 filed with the Japan Patent Office on June 4, 2021, and the entire contents of Japanese Patent Application No. 2021-094724 are incorporated into this application. .
１ 反射型マスクブランク
２ 基板
３ 多層反射膜
４ 吸収膜
５ 導電膜
４１ 開口パターン REFERENCE SIGNSLIST 1 reflective mask blank 2 substrate 3 multilayer reflective film 4 absorbing film 5 conductive film 41 aperture pattern
２ 基板
３ 多層反射膜
４ 吸収膜
５ 導電膜
４１ 開口パターン REFERENCE SIGNS
Claims (13)
- ガラス基板の一方の面にケイ素およびモリブデンを含有する多層反射膜を有する膜が形成された膜付き基板のガラス基板から、少なくとも前記多層反射膜を剥離するために用いられる薬液であって、
ｐＨ調整剤と、
メタ過ヨウ素酸、メタ過ヨウ素酸塩、オルト過ヨウ素酸、オルト過ヨウ素酸塩、過マンガン酸、過マンガン酸塩、およびＮ－メチルモルホリンＮ－オキシドからなる群から選択される少なくとも１つの酸化剤と、を含む、薬液。 A chemical solution used for peeling at least the multilayer reflective film from a glass substrate of a film-coated substrate having a film having a multilayer reflective film containing silicon and molybdenum formed on one surface of the glass substrate,
a pH adjuster;
at least one oxidation selected from the group consisting of metaperiodic acid, metaperiodate, orthoperiodic acid, orthoperiodate, permanganate, permanganate, and N-methylmorpholine N-oxide A drug solution, including an agent. - ｐＨが１０以上１６以下である、請求項１に記載の薬液。 The chemical solution according to claim 1, which has a pH of 10 or more and 16 or less.
- 前記ｐＨ調整剤は、水酸化ナトリウムまたは水酸化カリウムである、請求項１に記載の薬液。 The chemical solution according to claim 1, wherein the pH adjuster is sodium hydroxide or potassium hydroxide.
- 前記酸化剤は、メタ過ヨウ素酸、メタ過ヨウ素酸塩、オルト過ヨウ素酸またはオルト過ヨウ素酸塩である、請求項１に記載の薬液。 The chemical solution according to claim 1, wherein the oxidizing agent is metaperiodic acid, metaperiodate, orthoperiodic acid, or orthoperiodate.
- 前記酸化剤は、過マンガン酸または過マンガン酸塩である、請求項１に記載の薬液。 The chemical solution according to claim 1, wherein the oxidizing agent is permanganic acid or permanganate.
- クロム（ＶＩ）の酸化還元電位よりも高い酸化還元電位を有する金属およびそのイオンからなる群から選択される少なくとも１つを、前記酸化剤に対して０．０００１モル当量～１０モル当量さらに含む、請求項１に記載の薬液。 0.0001 molar equivalents to 10 molar equivalents of at least one selected from the group consisting of metals having a redox potential higher than that of chromium (VI) and ions thereof, with respect to the oxidizing agent; The chemical solution according to claim 1.
- キレート剤としてアミノカルボン酸系キレート剤、ヒドロキシ酸系キレート剤またはホスホン酸系キレート剤をさらに含む、請求項１に記載の薬液。 The drug solution according to claim 1, further comprising an aminocarboxylic acid-based chelating agent, a hydroxy acid-based chelating agent, or a phosphonic acid-based chelating agent as a chelating agent.
- ガラス基板の一方の面にケイ素およびモリブデンを含有する多層反射膜を有する膜が形成された膜付き基板を、ｐＨ調整剤と、メタ過ヨウ素酸、メタ過ヨウ素酸塩、オルト過ヨウ素酸、オルト過ヨウ素酸塩、過マンガン酸、過マンガン酸塩、およびＮ－メチルモルホリンＮ－オキシドからなる群から選択される少なくとも１つの酸化剤と、を含む薬液に接触させて、前記ガラス基板から少なくとも前記多層反射膜を剥離し、前記ガラス基板の前記多層反射膜が形成されていた面を再生することを特徴とする、膜付き基板の再生方法。 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, orthoperiodic acid, and orthoperiodic acid. and at least one oxidizing agent selected from the group consisting of periodate, permanganic acid, permanganate, and N-methylmorpholine N-oxide to remove at least the A method for regenerating a film-coated substrate, comprising peeling off the multilayer reflective film and regenerating the surface of the glass substrate on which the multilayer reflective film was formed.
- 前記膜付き基板は、前記多層反射膜の上に、ルテニウムを含有する保護膜を有する、請求項８に記載の膜付き基板の再生方法。 The method for recycling a film-coated substrate according to claim 8, wherein the film-coated substrate has a protective film containing ruthenium on the multilayer reflective film.
- 前記膜付き基板は、前記多層反射膜の上に、ルテニウム、タンタル、ニオブおよびホウ素からなる群から選択される少なくとも１つを含有する吸収膜を有する、請求項８に記載の膜付き基板の再生方法。 9. The regeneration of a film-coated substrate according to claim 8, wherein said film-coated substrate has an absorbing film containing at least one selected from the group consisting of ruthenium, tantalum, niobium and boron on said multilayer reflective film. Method.
- 前記膜付き基板は、前記多層反射膜が形成された面とは反対の面に、クロムまたはタンタルを含有する導電膜を有する、請求項８に記載の膜付き基板の再生方法。 The method for recycling a film-coated substrate according to claim 8, wherein the film-coated substrate has a conductive film containing chromium or tantalum on the surface opposite to the surface on which the multilayer reflective film is formed.
- 請求項８～１１のいずれか１項に記載の膜付き基板の再生方法により再生された前記ガラス基板の一方の面に、少なくとも、ケイ素およびモリブデンを含有する多層反射膜を形成することを含む、膜付き基板の製造方法。 Forming a multilayer reflective film containing at least silicon and molybdenum on one surface of the glass substrate regenerated by the method for regenerating a film-coated substrate according to any one of claims 8 to 11, A method for manufacturing a substrate with a film.
- 請求項８～１１のいずれか１項に記載の膜付き基板の再生方法により再生された前記ガラス基板の一方の面にケイ素およびモリブデンを含有する多層反射膜を形成することと、
前記多層反射膜の上にルテニウムまたはロジウムを含有する保護膜を形成することと、
前記保護膜の上にルテニウム、タンタル、クロム、イリジウム、ホウ素、ニオブ、レニウムおよびパラジウムからなる群から選択される少なくとも１つを含有する吸収膜を形成することと、
前記ガラス基板の前記多層反射膜が形成された面とは反対の面にクロム、タンタルおよびホウ素からなる群から選択される少なくとも１つを含有する導電膜を形成することと、
を含む、反射型マスクブランクの製造方法。 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 claims 8 to 11;
forming a protective film containing ruthenium or rhodium on the multilayer reflective film;
forming an absorbing film containing at least one selected from the group consisting of ruthenium, tantalum, chromium, iridium, boron, niobium, rhenium and palladium on the protective film;
forming a conductive film 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 multilayer reflective film is formed;
A method of manufacturing a reflective mask blank, comprising:
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| JP2007189174A (en) * | 2006-01-16 | 2007-07-26 | Nikon Corp | Multilayer-film reflector, method for regenerating same, and exposure apparatus |
| JP2011127221A (en) * | 2009-11-18 | 2011-06-30 | Hoya Corp | Method for regenerating substrate, method for producing mask blank, method for producing multilayer reflection film-fitted substrate and method for producing reflection type mask blank |
| JP2013174012A (en) * | 2012-02-02 | 2013-09-05 | Sematech Inc | Coating of shield surface in deposition system |
| JP2017181733A (en) * | 2016-03-30 | 2017-10-05 | Hoya株式会社 | Method for regenerating substrate with multilayer film, method for manufacturing substrate with multilayer reflection film and method for manufacturing reflection type mask blank |
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| JP2007189174A (en) * | 2006-01-16 | 2007-07-26 | Nikon Corp | Multilayer-film reflector, method for regenerating same, and exposure apparatus |
| JP2011127221A (en) * | 2009-11-18 | 2011-06-30 | Hoya Corp | Method for regenerating substrate, method for producing mask blank, method for producing multilayer reflection film-fitted substrate and method for producing reflection type mask blank |
| JP2013174012A (en) * | 2012-02-02 | 2013-09-05 | Sematech Inc | Coating of shield surface in deposition system |
| JP2017181733A (en) * | 2016-03-30 | 2017-10-05 | Hoya株式会社 | Method for regenerating substrate with multilayer film, method for manufacturing substrate with multilayer reflection film and method for manufacturing reflection type mask blank |
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