CN116500852A - Mask blank, transfer mask, method for manufacturing transfer mask, and method for manufacturing display device - Google Patents
Mask blank, transfer mask, method for manufacturing transfer mask, and method for manufacturing display device Download PDFInfo
- Publication number
- CN116500852A CN116500852A CN202310088032.0A CN202310088032A CN116500852A CN 116500852 A CN116500852 A CN 116500852A CN 202310088032 A CN202310088032 A CN 202310088032A CN 116500852 A CN116500852 A CN 116500852A
- Authority
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- China
- Prior art keywords
- film
- mask
- light
- pattern
- thin film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000012546 transfer Methods 0.000 title claims abstract description 196
- 238000000034 method Methods 0.000 title claims abstract description 95
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 75
- 239000000758 substrate Substances 0.000 claims abstract description 169
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 126
- 238000001228 spectrum Methods 0.000 claims abstract description 103
- 239000010936 titanium Substances 0.000 claims abstract description 96
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 65
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 63
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 62
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 59
- 239000010703 silicon Substances 0.000 claims abstract description 59
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 57
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 claims abstract description 37
- 229910007269 Si2P Inorganic materials 0.000 claims abstract description 29
- 239000002344 surface layer Substances 0.000 claims abstract description 19
- 239000010408 film Substances 0.000 claims description 444
- 239000010409 thin film Substances 0.000 claims description 239
- 238000005530 etching Methods 0.000 claims description 164
- 238000002834 transmittance Methods 0.000 claims description 88
- 230000010363 phase shift Effects 0.000 claims description 45
- 239000011651 chromium Substances 0.000 claims description 33
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 27
- 229910052804 chromium Inorganic materials 0.000 claims description 27
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 25
- 239000001301 oxygen Substances 0.000 claims description 25
- 229910052760 oxygen Inorganic materials 0.000 claims description 25
- 238000001039 wet etching Methods 0.000 claims description 15
- 230000001678 irradiating effect Effects 0.000 claims description 4
- 206010059866 Drug resistance Diseases 0.000 abstract description 29
- 230000007261 regionalization Effects 0.000 description 122
- 239000007789 gas Substances 0.000 description 61
- 230000000052 comparative effect Effects 0.000 description 55
- 238000000059 patterning Methods 0.000 description 50
- 230000008569 process Effects 0.000 description 36
- 229910021341 titanium silicide Inorganic materials 0.000 description 36
- 239000000463 material Substances 0.000 description 32
- 238000004544 sputter deposition Methods 0.000 description 30
- 238000004458 analytical method Methods 0.000 description 24
- 239000000203 mixture Substances 0.000 description 24
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 18
- 230000008859 change Effects 0.000 description 18
- 238000004140 cleaning Methods 0.000 description 16
- 238000005477 sputtering target Methods 0.000 description 16
- 230000015572 biosynthetic process Effects 0.000 description 15
- 230000000694 effects Effects 0.000 description 15
- 150000004767 nitrides Chemical class 0.000 description 14
- 239000010453 quartz Substances 0.000 description 13
- 230000003287 optical effect Effects 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 229910052786 argon Inorganic materials 0.000 description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 239000002131 composite material Substances 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- 238000005546 reactive sputtering Methods 0.000 description 9
- 239000010410 layer Substances 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 8
- 238000004381 surface treatment Methods 0.000 description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 6
- 229910001507 metal halide Inorganic materials 0.000 description 6
- 150000005309 metal halides Chemical class 0.000 description 6
- 229920002120 photoresistant polymer Polymers 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 230000001747 exhibiting effect Effects 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 239000011261 inert gas Substances 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 4
- 238000004380 ashing Methods 0.000 description 4
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 4
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- CXOWYMLTGOFURZ-UHFFFAOYSA-N azanylidynechromium Chemical compound [Cr]#N CXOWYMLTGOFURZ-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 3
- UFGZSIPAQKLCGR-UHFFFAOYSA-N chromium carbide Chemical compound [Cr]#C[Cr]C#[Cr] UFGZSIPAQKLCGR-UHFFFAOYSA-N 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 229910003470 tongbaite Inorganic materials 0.000 description 3
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 229910008484 TiSi Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229910052743 krypton Inorganic materials 0.000 description 2
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910052754 neon Inorganic materials 0.000 description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 2
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 2
- 239000012788 optical film Substances 0.000 description 2
- 238000000206 photolithography Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000005368 silicate glass Substances 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 239000005361 soda-lime glass Substances 0.000 description 2
- 238000010301 surface-oxidation reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- CGEORJKFOZSMEZ-MBZVMHRFSA-N (+)-sesamin monocatechol Chemical compound C1=C(O)C(O)=CC=C1[C@@H]1[C@@H](CO[C@@H]2C=3C=C4OCOC4=CC=3)[C@@H]2CO1 CGEORJKFOZSMEZ-MBZVMHRFSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- SJKRCWUQJZIWQB-UHFFFAOYSA-N azane;chromium Chemical compound N.[Cr] SJKRCWUQJZIWQB-UHFFFAOYSA-N 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical compound O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 description 1
- 150000001845 chromium compounds Chemical class 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002003 electron diffraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- FXNGWBDIVIGISM-UHFFFAOYSA-N methylidynechromium Chemical compound [Cr]#[C] FXNGWBDIVIGISM-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000985 reflectance spectrum Methods 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 238000000851 scanning transmission electron micrograph Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
- G03F1/26—Phase shift masks [PSM]; PSM blanks; Preparation thereof
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/001—General methods for coating; Devices therefor
- C03C17/002—General methods for coating; Devices therefor for flat glass, e.g. float glass
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
- C03C17/225—Nitrides
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
- C03C17/3429—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating
- C03C17/3435—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating comprising a nitride, oxynitride, boronitride or carbonitride
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
- C03C17/3429—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating
- C03C17/3441—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating comprising carbon, a carbide or oxycarbide
-
- 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
- G03F1/60—Substrates
-
- 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
- G03F1/62—Pellicles, e.g. pellicle assemblies, e.g. having membrane on support frame; 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
- G03F1/76—Patterning of masks by imaging
-
- 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
- G03F1/80—Etching
-
- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
- G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
- G09F9/33—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements being semiconductor devices, e.g. diodes
- G09F9/335—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements being semiconductor devices, e.g. diodes being organic light emitting diodes [OLED]
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/15—Deposition methods from the vapour phase
- C03C2218/154—Deposition methods from the vapour phase by sputtering
- C03C2218/155—Deposition methods from the vapour phase by sputtering by reactive sputtering
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/30—Aspects of methods for coating glass not covered above
- C03C2218/32—After-treatment
- C03C2218/328—Partly or completely removing a coating
- C03C2218/33—Partly or completely removing a coating by etching
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Theoretical Computer Science (AREA)
- Optics & Photonics (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Preparing Plates And Mask In Photomechanical Process (AREA)
- Electron Beam Exposure (AREA)
- Physical Vapour Deposition (AREA)
Abstract
The invention provides a mask blank, a transfer mask, a method for manufacturing the transfer mask, and a method for manufacturing a display device. The mask blank has high light resistance against exposure light including a wavelength of ultraviolet region, and has high drug resistance, and can form a good transfer pattern. The mask blank comprises a transparent substrate and a pattern forming film provided on the main surface of the transparent substrate, wherein the film contains titanium, silicon and nitrogen, and the photoelectron intensity of the Ti2P narrow spectrum having a binding energy of 455eV obtained by analyzing the inner region of the film by X-ray photoelectron spectroscopy is P N The photoelectron intensity of the Si2P narrow spectrum with the binding energy of 102eV is P S When meeting P N /P S The relation larger than 1.18 is that the internal region is a region of the film other than the vicinity region on the light-transmitting substrate side and the surface layer region on the opposite side to the light-transmitting substrate, and the nitrogen content in the internal region is 30 atomic% or more.
Description
Technical Field
The present invention relates to a mask blank, a transfer mask, a method for manufacturing a transfer mask, and a method for manufacturing a display device.
Background
In recent years, display devices such as FPDs (Flat Panel Display: flat panel displays) typified by OLEDs (Organic Light Emitting Diode: organic light emitting diodes) have been rapidly developed with an increase in the size of an interface and a wide field of view, and with a high definition and a high speed of display. One of the factors required for the high definition and high speed display is that an electronic circuit pattern such as a device or wiring having a high definition and high dimensional accuracy can be manufactured. Photolithography is often used for patterning of the electronic circuit for a display device. Therefore, a phase shift mask for manufacturing a display device and a transfer mask (photomask) such as a binary mask, in which a fine and high-precision pattern is formed, are required.
For example, patent document 1 discloses a photomask for exposing a fine pattern. Patent document 1 describes that a mask pattern formed on a transparent substrate of a photomask is constituted by a light transmitting portion that transmits light having an intensity that contributes to exposure in practice and a semi-transmitting portion that transmits light having an intensity that does not contribute to exposure in practice. Patent document 1 describes that the light passing through the boundary portion between the semi-transmissive portion and the transmissive portion is offset by a phase shift effect, thereby improving the contrast of the boundary portion. Patent document 1 describes that the photomask includes a thin film formed of a material mainly composed of nitrogen, metal, and silicon, and the silicon that is a component of the material constituting the thin film contains 34 to 60 atomic%.
Patent document 2 describes a halftone phase shift mask blank used for photolithography. Patent document 2 describes a mask blank having a substrate, an etching stop layer laminated on the substrate, and a phase shift layer laminated on the etching stop layer. Patent document 2 describes that a photomask having a phase shift of approximately 180 degrees at a selected wavelength of less than 500nm and a light transmittance of at least 0.001% can be manufactured using the mask blank.
Patent document 3 describes a photomask blank having a thin film for forming a pattern on a transparent substrate. Patent document 3 describes that a photomask blank is a photomask original for forming a transfer pattern on a transparent substrate by wet etching a thin film for pattern formation. Patent document 3 describes that the thin film for patterning of the photomask blank contains a transition metal and silicon and has a columnar structure.
Prior art literature
Patent literature
Patent document 1: (Japanese patent No. 2966369)
Patent document 2: japanese patent application laid-open No. 2005-522740
Patent document 3: japanese patent application laid-open No. 2020-95248
Disclosure of Invention
Technical problem to be solved by the invention
As a transfer mask used in the production of high definition (1000 ppi or more) flat panels in recent years, in order to enable high resolution pattern transfer, a transfer mask is required in which a transfer pattern including a fine pattern forming thin film pattern having an aperture of 6 μm or less and a line width of 4 μm or less is formed. Specifically, a transfer mask having a transfer pattern including a fine pattern having a diameter or width of 1.5 μm is required.
On the other hand, since a transfer mask obtained by patterning a pattern forming film of a mask blank is repeatedly used for pattern transfer to a transfer object, it is desirable that the actual pattern transfer also has high light resistance (ultraviolet light resistance) against the ultraviolet rays envisaged. Further, since the transfer mask is repeatedly cleaned at the time of manufacturing and at the time of using the mask, it is also desired to improve the cleaning resistance (chemical resistance) of the mask.
However, it has been difficult to produce a mask blank having a thin film for pattern formation which satisfies the transmittance requirement for exposure light having a wavelength including the ultraviolet region, and the ultraviolet light resistance (hereinafter simply referred to as "light resistance") and drug resistance requirement.
The present invention has been made to solve the above-described problems. That is, an object of the present invention is to provide a mask blank which has high light resistance to exposure light having a wavelength including an ultraviolet region, and which has high chemical resistance and can form a good transfer pattern.
Further, an object of the present invention is to provide a transfer mask having high light resistance to exposure light having a wavelength including an ultraviolet region, high chemical resistance, and a good transfer pattern, a method for manufacturing the transfer mask, and a method for manufacturing a display device.
Technical scheme for solving technical problems
As a technical means for solving the above problems, the present invention has the following configuration.
(constitution 1) A mask blank comprising a light-transmitting substrate and a pattern-forming film provided on a main surface of the light-transmitting substrate, characterized in that,
the film contains titanium, silicon and nitrogen,
binding energy in a narrow spectrum of Ti2p obtained by analysis of an inner region of the film by X-ray photoelectron spectroscopy is 455eVThe photoelectron intensity is P N The photoelectron intensity of 102eV of the binding energy in the Si2P narrow spectrum is P S When meeting P N /P S A relationship greater than 1.18,
the inner region is a region of the film other than a vicinity region on the light-transmitting substrate side and a surface layer region on the opposite side of the light-transmitting substrate,
the nitrogen content in the internal region is 30 atomic% or more.
(constitution 2) the mask blank according to the constitution 1, characterized in that,
an photoelectron intensity P of 461eV which makes the binding energy in the Ti2P narrow spectrum NU When meeting P NU /P S Greater than 1.05.
(constitution 3) the mask blank according to constitution 1 or 2, characterized in that,
the ratio of the titanium content in the inner region to the total content of titanium and silicon is 0.05 or more.
(constitution 4) the mask blank according to any one of constitution 1 to 3,
the total content of titanium, silicon and nitrogen in the internal region is 90 at% or more.
(constitution 5) the mask blank according to any one of constitution 1 to 4,
the oxygen content of the inner region is 7 at% or less.
(constitution 6) the mask blank according to any one of constitution 1 to 5,
the surface layer region on the side opposite to the light-transmitting substrate side is a region extending from the surface on the side opposite to the light-transmitting substrate side to a depth of 10 nm.
(constitution 7) the mask blank according to any one of constitution 1 to 6,
the vicinity area on the light-transmitting substrate side is an area extending from the surface on the light-transmitting substrate side to a depth of 10nm on the opposite side to the light-transmitting substrate.
(constitution 8) the mask blank according to any one of constitution 1 to 7,
the thin film is a phase-shifting film,
the phase shift film has a transmittance of 1% or more with respect to light having a wavelength of 365nm, and a phase difference of 150 DEG to 210 DEG with respect to light having a wavelength of 365 nm.
(constitution 9) the mask blank according to any one of constitution 1 to 8,
an etching mask film having a different etching selectivity with respect to the thin film is provided on the thin film.
(constitution 10) the mask blank according to constitution 9, characterized in that,
the etching mask film contains chromium.
(constitution 11) a transfer mask comprising a light-transmitting substrate and a film provided on a main surface of the light-transmitting substrate and having a transfer pattern, characterized in that,
the film contains titanium, silicon and nitrogen,
an photoelectron intensity P of 455eV as a binding energy in a narrow spectrum of Ti2P obtained by analyzing an inner region of the film by X-ray photoelectron spectroscopy N The photoelectron intensity of 102eV of the binding energy in the Si2P narrow spectrum is P S When meeting P N /P S A relationship greater than 1.18,
the inner region is a region of the film other than a vicinity region on the light-transmitting substrate side and a surface layer region on the opposite side of the light-transmitting substrate,
the nitrogen content in the internal region is 30 atomic% or more.
(constitution 12) the transfer mask according to constitution 11, characterized in that,
an photoelectron intensity P of 461eV which makes the binding energy in the Ti2P narrow spectrum NU When meeting P NU /P S Greater than 1.05.
(constitution 13) the transfer mask according to constitution 11 or 12, characterized in that,
the ratio of the titanium content in the inner region to the total content of titanium and silicon is 0.05 or more.
(constitution 14) the transfer mask according to any one of constitutions 11 to 13,
the total content of titanium, silicon and nitrogen in the internal region is 90 at% or more.
(constitution 15) the transfer mask according to any one of constitutions 11 to 14,
the oxygen content of the inner region is 7 at% or less.
(constitution 16) the transfer mask according to any one of constitution 11 to 15,
the surface layer region on the side opposite to the light-transmitting substrate side is a region extending from the surface on the side opposite to the light-transmitting substrate side to a depth of 10 nm.
(constitution 17) the transfer mask according to any one of constitution 11 to 16,
the vicinity area on the light-transmitting substrate side is an area extending from the surface on the light-transmitting substrate side to a depth of 10nm on the opposite side to the light-transmitting substrate.
(constitution 18) the transfer mask according to any one of constitution 11 to 17,
the thin film is a phase-shifting film,
the phase shift film has a transmittance of 1% or more with respect to light having a wavelength of 365nm, and a phase difference of 150 DEG to 210 DEG with respect to light having a wavelength of 365 nm.
(constitution 19) A method for producing a transfer mask, comprising:
a step of preparing a mask blank constituting any one of 1 to 8;
forming a resist film having a transfer pattern on the thin film;
and performing wet etching using the resist film as a mask, thereby forming a transfer pattern on the thin film.
(constitution 20) A method for producing a transfer mask, comprising:
preparing the mask blank of 9 or 10;
forming a resist film having a transfer pattern on the etching mask film;
performing wet etching using the resist film as a mask, and forming a transfer pattern on the etching mask film;
And performing wet etching using the etching mask film having the transfer pattern formed thereon as a mask, thereby forming a transfer pattern on the thin film.
(constitution 21) A method for manufacturing a display device, comprising:
a step of placing the transfer mask according to any one of claims 11 to 18 on a mask stage of an exposure apparatus;
and a step of irradiating the transfer mask with exposure light to transfer the transfer pattern to a resist film provided on the display device substrate.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, it is possible to provide a mask blank having high light resistance against exposure light including a wavelength of an ultraviolet region and having high drug resistance, and capable of forming a good transfer pattern.
Further, according to the present invention, it is possible to provide a transfer mask, a method for manufacturing a transfer mask, and a method for manufacturing a display device, which have high light resistance against exposure light having a wavelength including an ultraviolet region, and which have high chemical resistance and good transfer patterns.
Drawings
Fig. 1 is a schematic cross-sectional view showing a film structure of a mask blank according to an embodiment of the present invention.
Fig. 2 is a schematic cross-sectional view showing other film structures of a mask blank according to an embodiment of the present invention.
Fig. 3 is a schematic cross-sectional view showing a process for manufacturing a transfer mask according to an embodiment of the present invention.
Fig. 4 is a schematic cross-sectional view showing another process for manufacturing a transfer mask according to an embodiment of the present invention.
Fig. 5 is a graph showing the result (Ti 2p narrow spectrum) of X-ray photoelectron spectroscopy analysis with respect to the phase shift film of the mask blank according to each example of the present invention.
FIG. 6 is a graph showing the result (Si 2p narrow spectrum) of X-ray photoelectron spectroscopy analysis with respect to the phase shift film of the mask blank according to each example of the present invention.
FIG. 7 is a graph showing the results (Ti 2p narrow spectrum) of X-ray photoelectron spectroscopy analysis performed on the phase shift film of the mask blank of each comparative example of the present invention.
FIG. 8 is a graph showing the results (Si 2p narrow spectrum) of X-ray photoelectron spectroscopy analysis performed on the phase shift film of the mask blank of each comparative example of the present invention.
Description of the reference numerals
10 masking the blank; a 20-transparent substrate; 30a pattern forming film; 30a film pattern; 40 etching the mask film; 40a first etching mask film pattern; 40b a second etch mask film pattern; 50 a first resist film pattern; a second resist film pattern 60; 100 transfer mask.
Detailed Description
First, the process of the present invention will be described. The present inventors have conducted intensive studies on a structure of a mask blank having high light resistance and high drug resistance with respect to exposure light having a wavelength in the ultraviolet region (hereinafter, may be simply referred to as "exposure light"), and capable of forming a good transfer pattern. The present inventors have studied to use a titanium silicide-based material for a material of a thin film pattern of a transfer mask used for manufacturing a display device such as FPD (Flat Panel Display). The thin film of titanium silicide material has good optical properties and good drug resistance. On the other hand, although it has been considered that a thin film of a titanium silicide material has good characteristics in terms of resistance to irradiation with exposure light (exposure light including the wavelength of ultraviolet ray region), it has been revealed that light resistance with respect to exposure light may be greatly reduced. Accordingly, the present inventors have studied at various angles about differences between a thin film of a titanium silicide material having high light resistance to exposure light and a thin film of a titanium silicide material having low light resistance to exposure light. First, the inventors of the present invention studied the relationship between the composition of a thin film and the light resistance to exposure light by analysis using X-ray photoelectron spectroscopy (XPS: X-Ray Photoelectron Spectroscopy), but did not obtain a clear relationship between the composition of a thin film and the light resistance. Further, although observation of a cross-sectional SEM image, a plane STEM image, and an electron diffraction image were performed, no clear correlation was obtained between the light resistance and the SEM image.
As a result of further intensive studies, the inventors of the present invention have found that, when Ti2p narrow spectrum and Si2p narrow spectrum obtained by X-ray photoelectron spectroscopy (XPS) analysis are observed with respect to the inner region of the thin film for pattern formation, the difference in light resistance is visible even when the overall behaviors of the Ti2p narrow spectrum and the Si2p narrow spectrum are close (see the narrow spectrum of the third and fourth embodiments shown in fig. 5 and 6, and the narrow spectrum of the first comparative example shown in fig. 7 and 8).
As a result of further investigation, it was found that when the film of titanium silicide material having a nitrogen content of 30 atomic% or more was formed in the inner region thereof, the photoelectron strength (photoelectron strength with a binding energy of 455 eV) P corresponding to the Ti2P 3/2 TiN bond of Ti2P narrow spectrum N Divided by Si with Si2p narrow spectrum 3 N 4 Bond-corresponding photoelectron intensity (photoelectron intensity with binding energy of 102 eV) P S When the ratio satisfies the condition that the ratio is larger than 1.18, it is concluded that the light resistance is high with respect to exposure light.
The results of the above intensive studies have led to the mask blanks of the present invention. Specifically, the mask blank of the present invention is a mask blank comprising a light-transmitting substrate and a pattern-forming film provided on a main surface of the light-transmitting substrate, wherein the film contains titanium, silicon and nitrogen, and has an photoelectron intensity P of 455eV as a binding energy in a narrow spectrum of Ti2P obtained by analysis of an inner region of the film by X-ray photoelectron spectroscopy N The photoelectron intensity of the Si2P narrow spectrum with the binding energy of 102eV is P S When meeting P N /P S Greater than 1.18, the inner region being the film except the light-transmitting substrate sideThe nitrogen content in the inner region is 30 atomic% or more in the vicinity region and the region other than the surface layer region on the opposite side of the light-transmitting substrate.
Next, embodiments of the present invention will be specifically described with reference to the drawings. The following embodiments are merely modes for embodying the present invention, and are not intended to limit the present invention to this range.
Fig. 1 is a schematic diagram showing a film structure of a mask blank 10 according to the present embodiment. The mask blank 10 shown in fig. 1 has: a light-transmitting substrate 20, a pattern-forming film 30 (e.g., a phase shift film) formed on the light-transmitting substrate 20, and an etching mask film (e.g., a light-shielding film) 40 formed on the pattern-forming film 30.
Fig. 2 is a schematic diagram showing a film structure of a mask blank 10 according to other embodiments. The mask blank 10 shown in fig. 2 has: a light-transmitting substrate 20, and a pattern-forming film 30 (e.g., a phase shift film) formed on the light-transmitting substrate 20.
In the present specification, the "film for pattern formation 30" refers to a film (hereinafter, may be simply referred to as "film 30") in which a predetermined fine pattern is formed on the transfer mask 100 such as a light shielding film and a phase shift film. In the description of the present embodiment, a phase shift film is sometimes used as a specific example of the thin film for pattern formation 30, and a phase shift film pattern is sometimes used as a specific example of the thin film pattern for pattern formation 30a (hereinafter, may be simply referred to as "thin film pattern 30 a"). The light shielding film and light shielding film pattern, the transmittance adjustment film pattern, and other pattern forming films 30 and pattern forming film patterns 30a are similar to the phase shift film and phase shift film pattern.
Next, the light-transmitting substrate 20, the pattern-forming thin film 30 (e.g., a phase shift film), and the etching mask film 40 constituting the mask blank 10 for manufacturing a display device according to the present embodiment will be specifically described.
Light-transmitting substrate 20
The light-transmitting substrate 20 is transparent to the exposure light. The transparent substrate 20 has a surface reflection loss of 85% or more with respect to exposure lightThe transmittance is preferably 90% or more. The light-transmitting substrate 20 is formed of a material containing silicon and oxygen, and may be made of synthetic quartz glass, aluminum silicate glass, soda lime glass, and low thermal expansion glass (SiO 2 -TiO 2 Glass, etc.) and the like. When the light-transmitting substrate 20 is made of low thermal expansion glass, the positional change of the thin film pattern 30a due to thermal deformation of the light-transmitting substrate 20 can be suppressed. The light-transmitting substrate 20 used for the display device is generally a rectangular substrate. Specifically, a substrate having a short side length of 300mm or more of the main surface (surface on which the pattern forming film 30 is formed) of the light-transmitting substrate 20 may be used. In the mask blank 10 of the present embodiment, a large-sized light-transmitting substrate 20 having a major surface with a short side length of 300mm or more may be used. Using the mask blank 10 of the present embodiment, a transfer mask 100 having a transfer pattern including a fine pattern forming thin film pattern 30a having a width dimension and/or a diameter dimension of less than 2.0 μm on a light-transmitting substrate 20 can be manufactured, for example. By using the transfer mask 100 according to the present embodiment described above, a transfer pattern including a predetermined fine pattern can be stably transferred to a transfer object.
Pattern forming film 30
The thin film 30 for patterning (hereinafter, abbreviated as "thin film 30 for patterning of the present embodiment") of the mask blank 10 for manufacturing a display device of the present embodiment (hereinafter, abbreviated as "mask blank 10 of the present embodiment" in some cases) is formed of a material containing titanium (Ti), silicon (Si) and nitrogen (N). The pattern forming film 30 may be a phase shift film having a phase shift function.
The patterning thin film 30 contains nitrogen. In the titanium silicide, nitrogen as a light element component has an effect of not lowering the refractive index as compared with oxygen as a light element component. Therefore, the film for pattern formation 30 can be thinned by containing nitrogen to obtain a desired phase difference (also referred to as a phase shift amount). The nitrogen content in the thin film for pattern formation 30 is preferably 30 at% or more, more preferably 40 at% or more. On the other hand, the nitrogen content is preferably 60 at% or less, more preferably 55 at% or less. Since the nitrogen content in the thin film 30 is large, an excessive increase in transmittance with respect to exposure light can be suppressed.
The interior of the pattern forming film 30 is divided into three regions, i.e., a vicinity region, an interior region, and a surface region, in order from the light-transmitting substrate 20 side. The vicinity region is a region extending from the interface between the patterning thin film 30 and the light-transmitting substrate 20 to a depth of 10nm (more preferably, a depth of 5nm, and still more preferably, a depth of 4 nm) on the surface side opposite to the light-transmitting substrate 20 (i.e., the surface layer region side). When the X-ray photoelectron spectroscopy is performed with respect to the vicinity, the influence of the light-transmitting substrate 20 existing thereunder is likely to occur, and the accuracy of the maximum peak of the photoelectron intensity of the Ti2p narrow spectrum and the Si2p narrow spectrum in the obtained vicinity is low.
The surface layer region is a region extending from the surface on the opposite side of the light-transmitting substrate 20 toward the light-transmitting substrate 20 to a depth of 10nm (more preferably a depth of 5nm, and further preferably a depth of 4 nm). When another film such as the etching mask film 40 is present above the surface layer region, the surface layer region is a region susceptible to the film. In the case where no other film is present above the surface layer region, the surface layer region is a region containing oxygen taken in from the surface of the thin film for patterning 30. Therefore, when the X-ray photoelectron spectroscopy is performed with respect to the surface layer region, the accuracy of the maximum peak of the photoelectron intensity of the Ti2p narrow spectrum and the Si2p narrow spectrum of the obtained surface layer region is low.
The inner region is a region of the film 30 for pattern formation other than the vicinity region and the surface layer region. A narrow spectrum of Ti2P and a narrow spectrum of Si2P obtained by analysis of the internal region by X-ray photoelectron spectroscopy have a photoelectron intensity P at a binding energy of 455eV N The photoelectron intensity of 102eV is P S When meeting P N /P S Greater than 1.18.
Here, the binding energy of 455eV corresponds to that of TiN bonds in the Ti2p 3/2 peak, and the binding energy of 102eV corresponds to that of Si in the peak of Si2p 3 N 4 Binding energy of bond (see fig. 5 to 8).
The invention is characterized in thatThe inventors are directed to P N /P S The relationship with the light resistance was estimated as follows.
When the thin film 30 for pattern formation is made of a titanium silicide material containing titanium and silicon, the titanium (Ti) in the thin film 30 mainly includes titanium existing as Ti monomers and titanium existing in a TiN bonding state (see fig. 5 and 7). As shown in fig. 5 and 7, in the peak of Ti2p 3/2, the binding energy of Ti present in the bonding state of TiN is higher than that of titanium present in the Ti monomer. Therefore, ti in a bonded state of TiN is resistant to a change in the state of Ti due to irradiation of exposure light including ultraviolet rays, and is less likely to cause a change in transmittance due to a change in the state of Ti, as compared with Ti in a Ti monomer. On the other hand, since nitrogen in the thin film 30 is bonded to silicon (Si) in addition to titanium (Ti), it is considered that in the case where the content of nitrogen is small, the amount of nitrogen bonded to titanium is relatively small, and titanium present as Ti monomer increases. When the nitrogen content is 30 at% or more, it is considered that Si which is stoichiometrically stable exists to some extent 3 N 4 Si present in the bonded state of (a). In this case, when P is satisfied N /P S In the case of the relation larger than 1.18, in the thin film 30, in the state where Si is bonded to nitrogen to some extent, ti is considered to exist in a bonding state of TiN in a certain proportion or more, and thus, it is presumed that the film has high light resistance against exposure light including ultraviolet rays. However, this presumption is based on the knowledge of the present stage and is not intended to limit the scope of the claims of the present invention in any way.
Even if a composition analysis such as an X-ray photoelectron spectroscopy (XPS) analysis is performed in the vicinity of the interface with the light-transmitting substrate 20, the composition of the light-transmitting substrate 20 is inevitably affected, and therefore it is difficult to specify a numerical value for the composition and the number of existence of bonds. However, it can be assumed that the same configuration as the above-described internal region is made.
P N /P S More preferably 1.19 or more, and still more preferably 1.20 or more.
In addition, P N /P S Preferably 3.00 or less, more preferably 2.50 or less, and still more preferably 2.00 or less.
Further, the narrow spectrum of Ti2P obtained by analysis of the internal region by X-ray photoelectron spectroscopy had a photoelectron intensity P at which the binding energy was 461eV NU When it is, preferably, P is satisfied NU /P S A relation greater than 1.05 is more preferably 1.10 or more, and still more preferably 1.15 or more.
Here, the binding energy of 461eV corresponds to the binding energy of TiN bond at the peak of Ti2p 1/2 (see fig. 5 and 7).
As described above, even in the peak of Ti2p 1/2, the binding energy of Ti present in the bonding state of TiN is higher than that of Ti present in the monomer. Therefore, P is satisfied when the nitrogen content is 30 at% or more NU /P S In the case of the relation larger than 1.10, in the state where Si is bonded to nitrogen to some extent, ti is considered to exist in a bonded state of TiN in a certain proportion or more, and therefore, it is presumed to have high light resistance against exposure light including ultraviolet rays. However, this presumption is based on the knowledge of the present stage and is not intended to limit the scope of the claims of the present invention in any way.
In addition, P NU /P S Preferably 2.50 or less, more preferably 2.00 or less.
Further, the narrow spectrum of Ti2P and the narrow spectrum of Si2P obtained by analysis of the internal region by X-ray photoelectron spectroscopy preferably satisfy (P N +P NU )/P S Greater than 2.22.
As described above, in any of the peak value of Ti2p 3/2 and the peak value of Ti2p 1/2, the binding energy of Ti in the bonding state of TiN and Ti in the bonding state of TiO is higher than that of Ti in the bonding state of a single body. Therefore, the nitrogen content is 30 at% or more and P is satisfied NU /P S In the case of the relation larger than 1.10, in the state where Si is bonded to nitrogen to some extent, ti is considered to exist in a bonded state of TiN in a certain proportion or more, and thus, it is presumed to have high light resistance against exposure light including ultraviolet rays. However, this presumption is based on the knowledge of the present stage and is not intended to limit the scope of the claims of the present invention in any way.
(P N +P NU )/P S More preferably 2.25 or more, and still more preferably 2.30 or more.
In addition, (P) N +P NU )/P S Preferably 5.00 or less, more preferably 4.50 or less.
Further, the narrow spectrum of Ti2P and the narrow spectrum of Si2P obtained by analysis of the internal region by X-ray photoelectron spectroscopy are preferably such that the photoelectron intensity at which the binding energy is 453eV is P TS When meeting P N /P TS Greater than 2.13.
Here, 453eV of TiSi has a binding energy corresponding to the peak of Ti2p 3/2 2 Binding energy of bond (see fig. 5 and 7).
P N /P TS More preferably 2.20 or more, and still more preferably 2.50 or more.
P N /P TS Preferably 4.00 or less, more preferably 3.50 or less.
Further, the narrow spectrum of Ti2P and the narrow spectrum of Si2P obtained by analysis of the internal region by X-ray photoelectron spectroscopy are preferably obtained at a photoelectron intensity P such that the binding energy is 454eV T When (P) is satisfied N +P T )/P TS Greater than 3.53.
Here, the binding energy of 454eV corresponds to the binding energy of Ti monomer of the peak of Ti2p 3/2 (see fig. 5 and 7).
(P N +P T )/P TS More preferably 3.60 or more, and still more preferably 3.90 or more.
(P N +P T )/P TS Preferably 5.50 or less, more preferably 5.00 or less.
The ratio of the titanium content to the total content of titanium and silicon (hereinafter sometimes referred to as Ti/[ Ti+Si ] ratio) in the internal region is preferably 0.05 or more, more preferably 0.10 or more. When the ratio of Ti/[ ti+si ] in the internal region is too small, it is difficult to obtain the advantages of optical characteristics and drug resistance by using a titanium silicide-based material for the thin film for pattern formation 30. On the other hand, the ratio of Ti/[ Ti+Si ] in the internal region is preferably 0.50 or less, more preferably 0.45 or less.
The total content of titanium, silicon, and nitrogen in the internal region is preferably 90 at% or more, more preferably 95 at% or more. In the internal region, when the content of elements other than titanium, silicon, and nitrogen increases, various characteristics such as optical characteristics, drug resistance, light resistance to ultraviolet rays, and the like may be degraded.
The thin film for patterning 30 may contain oxygen within a range where the performance of the thin film for patterning 30 does not deteriorate. Oxygen as a light element component has an effect of lowering the extinction coefficient as compared with nitrogen as a light element component. However, when the oxygen content of the thin film 30 for forming a pattern is large, a cross section of a fine pattern close to vertical and a high mask cleaning resistance may be adversely affected. Therefore, the oxygen content of the pattern forming film 30 is preferably 7 at% or less, and more preferably 5 at% or less. The patterning thin film 30 may not contain oxygen.
As shown in fig. 5 and 7, the photoelectron intensity with the binding energy 453eV corresponds to TiSi in the peak of Ti2p 3/2 2 Bond energy, photoelectron intensity of 454eV corresponds to that of Ti monomer in peak of Ti2p 3/2, bond energy of 455eV corresponds to that of TiN bond in peak of Ti2p 3/2, bond energy of 456.9eV corresponds to that of TiO bond in peak of Ti2p 3/2, and bond energy of 458.5eV corresponds to that of TiO in peak of Ti2p 3/2 2 The binding energy of the bond, 460eV, corresponds to the binding energy of the Ti monomer in the peak of Ti2p 1/2 and 461eV corresponds to the binding energy of the TiN bond in the peak of Ti2p 1/2.
In addition to the above-described oxygen and nitrogen, the thin film 30 for patterning may contain other light element components such as carbon and helium in order to control the reduction of film stress and/or wet etching rate.
The atomic ratio of titanium to silicon contained in the thin film for pattern formation 30 is preferably in the range of titanium: silicon=1:1 to 1:19. When the amount is within this range, the effect of suppressing the decrease in wet etching rate during patterning of the patterning thin film 30 can be increased. In addition, the cleaning resistance of the pattern forming film 30 can be improved, and the transmittance can be easily improved. From the viewpoint of improving the cleaning resistance of the thin film for pattern formation 30, the atomic ratio of titanium to silicon (titanium: silicon) contained in the thin film for pattern formation 30 is preferably in the range of 1:1 to 1:19, more preferably in the range of 1:1 to 1:11, and still more preferably in the range of 1:1 to 1:9.
The pattern forming film 30 may be formed of a plurality of layers or may be formed of a single layer. The patterning thin film 30 composed of a single layer is preferable because it is difficult to form an interface in the patterning thin film 30 and the cross-sectional shape is easy to control. On the other hand, the thin film 30 for pattern formation composed of a plurality of layers is preferable because it is easy to form a film or the like.
In order to secure optical performance, the film thickness of the thin film 30 for pattern formation is preferably 200nm or less, more preferably 180nm or less, and still more preferably 150nm or less. In order to ensure a function of generating a desired phase difference, the film thickness of the thin film for pattern formation 30 is preferably 80nm or more, more preferably 90nm or more.
Transmittance and phase difference of film for patterning 30
The mask blank 10 for manufacturing a display device according to the present embodiment is preferably a phase shift film having optical characteristics such that the transmittance is 1% or more and 80% or less and the phase difference is 150 degrees or more and 210 degrees or less with respect to the representative wavelength of exposure light (light having a wavelength of 365 nm). Unless otherwise specified, the transmittance in the present specification is converted based on the transmittance of the light-transmitting substrate (100%).
When the pattern forming film 30 is a phase shift film, the pattern forming film 30 has a function of adjusting reflectance (hereinafter, sometimes referred to as back surface reflectance) with respect to light incident from the light transmitting substrate 20 side and a function of adjusting transmittance and phase difference with respect to exposure light.
The transmittance of the pattern forming film 30 with respect to exposure light satisfies a value required as the pattern forming film 30. The transmittance of the thin film for pattern formation 30 is preferably 1% or more and 80% or less, more preferably 3% or more and 65% or less, and still more preferably 5% or more and 60% or less, with respect to light of a predetermined wavelength (hereinafter referred to as a representative wavelength) included in the exposure light. That is, when the exposure light is a composite light including light in a wavelength range of 313nm to 436nm, the thin film for pattern formation 30 has the transmittance with respect to light of a representative wavelength included in the wavelength range. For example, when the exposure light is a composite light including i-line, h-line, and g-line, the film 30 for patterning may have the transmittance described above with respect to any of the i-line, h-line, and g-line. The representative wavelength may be, for example, an i-line having a wavelength of 365 nm. By having the above characteristics with respect to the i-line, when the composite light including the i-line, the h-line, and the g-line is used as the exposure light, a similar effect can be expected with respect to the transmittance at the wavelength of the h-line and the g-line.
When the exposure light is monochromatic light obtained by cutting and selecting a certain wavelength range from a wavelength range of 313nm to 436nm by a filter or the like, and monochromatic light selected from a wavelength range of 313nm to 436nm, the pattern forming film 30 has the transmittance with respect to the monochromatic light of the single wavelength.
The transmittance may be measured using a phase shift measurement device or the like.
The phase difference of the pattern forming film 30 with respect to the exposure light satisfies a value required as the pattern forming film 30. The phase difference of the pattern forming film 30 is preferably 150 degrees or more and 210 degrees or less, more preferably 160 degrees or more and 200 degrees or less, and still more preferably 170 degrees or more and 190 degrees or less, with respect to the light of the representative wavelength included in the exposure light. By utilizing this property, the phase of the light of the representative wavelength included in the exposure light can be changed to 150 degrees or more and 210 degrees or less. Therefore, a phase difference of 150 degrees or more and 210 degrees or less occurs between the light of the representative wavelength transmitted through the pattern forming film 30 and the light of the representative wavelength transmitted through only the light transmitting substrate 20. That is, when the exposure light is a composite light including light in a wavelength range of 313nm to 436nm, the thin film for pattern formation 30 has the above-described phase difference with respect to light of a representative wavelength included in the wavelength range. For example, when the exposure light is a composite light including i line, h line, and g line, the film 30 for forming a pattern may have the above-described phase difference with respect to any line of the i line, h line, and g line. The representative wavelength may be, for example, an h-line having a wavelength of 405 nm. By having the above characteristics with respect to the h-line, even when the composite light including the i-line, the h-line, and the g-line is used as the exposure light, a similar effect can be expected with respect to the phase difference at the wavelengths of the i-line and the g-line.
The phase difference may be measured using a phase shift measurement device or the like.
The back surface reflectance of the pattern forming film 30 is 15% or less, preferably 10% or less in a wavelength region of 365nm to 436 nm. When the exposure light includes j lines (wavelength of 313 nm), the back surface reflectance of the pattern forming film 30 is preferably 20% or less, more preferably 17% or less, with respect to light in a wavelength range of 313nm to 436 nm. Further, it is preferably 15% or less. The back surface reflectance of the pattern forming film 30 is 0.2% or more in the wavelength region of 365nm to 436nm, and preferably 0.2% or more with respect to light in the wavelength region of 313nm to 436 nm.
The back reflectivity may be measured using a spectrophotometer or the like.
The thin film for pattern formation 30 can be formed by a known film formation method such as sputtering.
Etching mask film 40
The mask blank 10 for manufacturing a display device according to the present embodiment preferably has an etching mask film 40 having a different etching selectivity with respect to the thin film 30 for forming a pattern over the thin film 30 for forming a pattern.
The etching mask film 40 is disposed above the pattern forming film 30 and is formed of a material having etching resistance (etching selectivity different from that of the pattern forming film 30) with respect to the etching liquid for etching the pattern forming film 30. In addition, the etching mask film 40 may have a function of blocking transmission of exposure light. The etching mask film 40 may have a function of reducing the film surface reflectance so that the film surface reflectance of the pattern forming film 30 with respect to the light incident from the pattern forming film 30 side is 15% or less in a wavelength region of 350nm to 436 nm.
The etching mask film 40 is preferably made of a chromium-based material containing chromium (Cr). The etching mask film 40 is more preferably made of a material containing chromium and practically not containing silicon. The fact that silicon is not contained means that the silicon content is less than 2% (however, except for the composition inclined region of the interface of the thin film for pattern formation 30 and the etching mask film 40). More specifically, the chromium-based material may be chromium (Cr), or a material containing chromium (Cr) and at least one element selected from oxygen (O), nitrogen (N), and carbon (C). Examples of the chromium-based material include a material containing chromium (Cr), at least one element selected from oxygen (O), nitrogen (N) and carbon (C), and fluorine (F). For example, cr, crO, crN, crF, crCO, crCN, crON, crCON and CrCONF are examples of the material constituting the etching mask film 40.
The etching mask film 40 can be formed by a known film forming method such as a sputtering method.
When the etching mask film 40 has a function of blocking the transmission of exposure light, the optical density of the pattern forming thin film 30 and the etching mask film 40 is preferably 3 or more, more preferably 3.5 or more, and still more preferably 4 or more with respect to the exposure light. The optical concentration may be measured using a spectrophotometer, an OD meter, or the like.
The etching mask film 40 may be a single film having a uniform composition according to functions. In addition, the etching mask film 40 may be a plurality of films having different compositions. In addition, the etching mask film 40 may be a single film having a composition that continuously changes in the thickness direction.
The mask blank 10 of the present embodiment shown in fig. 1 has an etching mask film 40 on the thin film 30 for pattern formation. The mask blank 10 of the present embodiment includes a mask blank 10 having a structure in which an etching mask film 40 is provided on a thin film 30 for pattern formation, and a resist film is provided on the etching mask film 40.
Method for manufacturing mask blank 10
Next, a method for manufacturing the mask blank 10 according to the embodiment shown in fig. 1 will be described. The mask blank 10 shown in fig. 1 is manufactured by performing the following thin film forming process for pattern formation and etching mask film forming process. The mask blank 10 shown in fig. 2 is manufactured by a thin film forming process for pattern formation.
The following describes each step in detail.
Film Forming Process for Pattern formation
First, a light-transmitting substrate 20 is prepared. When the light-transmitting substrate 20 is transparent to exposure light, it may be made of a material selected from the group consisting of synthetic quartz glass, aluminum silicate glass, soda lime glass, and low thermal expansion glass (SiO 2 -TiO 2 Glass, etc.), etc.
Next, a thin film 30 for pattern formation is formed on the light-transmitting substrate 20 by sputtering.
The film 30 for patterning can be formed in a predetermined sputtering gas atmosphere using a predetermined sputtering target. The predetermined sputtering target is, for example, a sputtering target composed of a titanium silicide target containing titanium and silicon as main components of the material constituting the thin film 30 for pattern formation, or a titanium silicide target containing titanium, silicon, and nitrogen. The predetermined sputtering gas atmosphere is, for example, a sputtering gas atmosphere formed of an inert gas including at least one selected from the group consisting of helium, neon, argon, krypton, and xenon, or a sputtering gas atmosphere formed of the above inert gas, nitrogen, and a mixed gas including a gas selected from the group consisting of oxygen, carbon dioxide, nitric oxide, and nitrogen dioxide, as the case may be. The thin film 30 for pattern formation may be formed in a state where the gas pressure in the film formation chamber is 0.3Pa or more and 2.0Pa or less, preferably 0.43Pa or more and 0.9Pa or less, when sputtering is performed. Side etching at the time of pattern formation can be suppressed, and a high etching rate can be achieved. The atomic ratio of titanium to silicon in the titanium silicide target is preferably in the range of titanium: silicon=1:1 to 1:19 from the viewpoints of improvement of light resistance and drug resistance, adjustment of transmittance, and the like.
The composition and thickness of the pattern forming film 30 are adjusted so that the pattern forming film 30 has the above-described retardation and transmittance. The composition of the thin film 30 for patterning may be controlled by the content ratio of elements constituting the sputtering target (for example, the ratio of the content of titanium to the content of silicon), the composition and flow rate of the sputtering gas, and the like. The thickness of the pattern forming film 30 can be controlled by the sputtering power and the sputtering timeAnd the like. The patterning thin film 30 is preferably formed using a continuous sputtering apparatus. In the case where the sputtering apparatus is a continuous sputtering apparatus, the thickness of the thin film 30 for pattern formation can be controlled by the transport speed of the substrate. In this way, the thin film 30 for pattern formation is controlled so as to contain titanium, silicon and nitrogen, and the nitrogen content in the internal region of the thin film 30 is 30 at% or more, and the Ti2P narrow spectrum and the Si2P narrow spectrum satisfy a desired relationship (P N /P T Greater than 1.52), etc.).
When the thin film 30 for patterning is formed of a single film, the film formation process is performed only once by appropriately adjusting the composition and flow rate of the sputtering gas. When the thin film 30 for patterning is formed of a plurality of films having different compositions, the film formation process is performed a plurality of times by appropriately adjusting the composition and flow rate of the sputtering gas. The thin film 30 for pattern formation may be formed using targets having different content ratios of elements constituting the sputtering target. In the case of performing the film forming process a plurality of times, the sputtering power to be applied to the sputtering target may be changed for each film forming process.
Surface treatment Process
The thin film 30 for patterning may be formed of a titanium silicide material (titanium silicide oxynitride) containing oxygen in addition to titanium, silicon, and nitrogen. However, the oxygen content is more than 0 atomic% and 7 atomic% or less. In this way, when the thin film for patterning 30 contains oxygen, a surface treatment step of adjusting the oxidation state of the surface of the thin film for patterning 30 may be performed to the surface of the thin film for patterning 30 in order to prevent the etching solution from being immersed in the presence of titanium oxide. In the case where the thin film 30 for pattern formation is formed of titanium silicide nitride containing titanium, silicon, and nitrogen, the content of titanium oxide is smaller than that of the titanium silicide material containing oxygen. Therefore, in the case where the material of the thin film for pattern formation 30 is titanium silicide nitride, the surface treatment step may be performed or may not be performed.
Examples of the surface treatment step for adjusting the surface oxidation state of the pattern forming thin film 30 include a method of performing surface treatment with an acidic aqueous solution, a method of performing surface treatment with an alkaline aqueous solution, and a method of performing surface treatment with a drying treatment such as ashing.
Thus, the mask blank 10 of the present embodiment can be obtained.
Etching mask film Forming Process
The mask blank 10 of the present embodiment may further have an etching mask film 40. The following etching mask film formation process was also performed. The etching mask film 40 is preferably made of a material containing chromium and practically not containing silicon.
After the patterning thin film forming step, a surface treatment for adjusting the surface oxidation state of the surface of the patterning thin film 30 is performed as necessary, and then an etching mask film 40 is formed on the patterning thin film 30 by a sputtering method. The etching mask film 40 is preferably formed using a continuous sputtering apparatus. In the case where the sputtering apparatus is a continuous sputtering apparatus, the thickness of the etching mask film 40 can be controlled by the transport speed of the transparent substrate 20.
The etching mask film 40 can be formed using a sputtering target including chromium or a chromium compound (chromium oxide, chromium nitride, chromium carbide, chromium oxynitride, chromium carbonitride oxide, or the like) in a sputtering gas atmosphere formed of an inert gas or in a sputtering gas atmosphere formed of a mixed gas of an inert gas and an active gas. The inert gas may include, for example, at least one selected from the group consisting of helium, neon, argon, krypton, and xenon. The reactive gas may include at least one selected from the group consisting of oxygen, nitrogen, nitric oxide gas, nitrogen dioxide gas, carbon dioxide gas, hydrocarbon-based gas, and fluorine-based gas. Examples of the hydrocarbon gas include methane gas, ethane gas, propane gas, and styrene gas. By adjusting the gas pressure in the film forming chamber during sputtering, the etching mask film 40 can have a columnar structure in the same manner as the thin film 30 for pattern formation. This suppresses side etching at the time of pattern formation described later, and can realize a high etching rate.
When the etching mask film 40 is formed of a single film having a uniform composition, the film formation process is performed only once without changing the composition and flow rate of the sputtering gas. In the case where the etching mask film 40 is formed of a plurality of films having different compositions, the composition and flow rate of the sputtering gas are changed every film formation process, and the film formation process described above is performed a plurality of times. When the etching mask film 40 is formed of a single film having a continuously variable composition in the thickness direction, the composition and flow rate of the sputtering gas are changed with the passage of time of the film forming process, and the film forming process is performed only once.
Thus, the mask blank 10 of the present embodiment having the etching mask film 40 can be obtained.
Since the mask blank 10 shown in fig. 1 has the etching mask film 40 on the thin film 30 for pattern formation, the etching mask film forming step is performed at the time of manufacturing the mask blank 10. In the case of manufacturing the mask blank 10 having the etching mask film 40 on the pattern forming thin film 30 and the resist film on the etching mask film 40, the resist film is formed on the etching mask film 40 after the etching mask film forming step. In the mask blank 10 shown in fig. 2, when the mask blank 10 having a resist film on the thin film for pattern formation 30 is manufactured, the resist film is formed after the thin film for pattern formation step.
The mask blank 10 of the embodiment shown in fig. 1 has an etching mask film 40 formed on a thin film 30 for pattern formation. In addition, the mask blank 10 of the embodiment shown in fig. 2 is formed with a thin film 30 for pattern formation. In any case, the thin film 30 for pattern formation contains titanium, silicon, and nitrogen, and the nitrogen content in the internal region of the thin film 30 is 30 atomic% or more, and the Ti2P narrow spectrum and the Si2P narrow spectrum satisfy a desired relationship (P N /P S Greater than 1.18), etc.).
The mask blank 10 of the embodiment shown in fig. 1 and 2 has high light resistance and high drug resistance with respect to exposure light including a wavelength of an ultraviolet region. In addition, when patterning the thin film 30 for pattern formation by wet etching, etching in the film thickness direction can be promoted, while side etching can be suppressed. Therefore, the patterned thin film pattern 30a has a favorable cross-sectional shape and a desired transmittance (e.g., high transmittance). By using the mask blank 10 of the embodiment, the thin film pattern 30a for pattern formation can be formed in a short etching time. Further, even after the exposure light having a wavelength including the ultraviolet region is accumulated, the thin film pattern 30a for pattern formation, which can maintain the exposure transfer characteristic within a desired range, can be formed.
Therefore, by using the mask blank 10 of the present embodiment, it is possible to manufacture the transfer mask 100 having high light resistance to exposure light having a wavelength including an ultraviolet region, high chemical resistance, and capable of transferring the high-definition pattern forming thin film pattern 30a with high accuracy.
Method for manufacturing transfer mask 100
Next, a method for manufacturing the transfer mask 100 according to the present embodiment will be described. The transfer mask 100 has the same technical features as the mask blank 10. The matters related to the transparent substrate 20, the pattern forming, the thin film 30, and the etching mask film 40 of the transfer mask 100 are the same as those of the mask blank 10.
Fig. 3 is a schematic diagram showing a method for manufacturing the transfer mask 100 according to the present embodiment. Fig. 4 is a schematic diagram showing another method of manufacturing the transfer mask 100 according to the present embodiment.
Method for manufacturing transfer mask 100 shown in FIG. 3
The method for manufacturing the transfer mask 100 shown in fig. 3 is a method for manufacturing the transfer mask 100 using the mask blank 10 shown in fig. 1. The method for manufacturing the transfer mask 100 shown in fig. 3 includes: a step of preparing the mask blank shown in fig. 1; forming a resist film on the etching mask film 40, wet etching the etching mask film 40 using the resist film pattern formed by the resist film as a mask, and forming an etching mask film pattern (first etching mask film pattern 40 a) on the pattern forming film 30; a step of forming a transfer pattern on the transparent substrate 20 by wet etching the pattern forming thin film 30 using the etching mask film pattern (first etching mask film pattern 40 a) as a mask. The pattern for transfer in the present specification is obtained by patterning at least one optical film formed on the light-transmitting substrate 20. The optical film may be the thin film 30 for pattern formation and/or the etching mask film 40, and may include other films (a light shielding film, a film for suppressing reflection, a conductive film, and the like). That is, the transfer pattern may include a patterned thin film for forming a pattern and/or an etching mask film, or may include another patterned film.
Specifically, the method for manufacturing the transfer mask 100 shown in fig. 3 forms a resist film on the etching mask film 40 of the mask blank 10 shown in fig. 1. Next, a resist film pattern 50 is formed by performing patterning and development of a desired pattern on the resist film (see fig. 3 (a), a step of forming the first resist film pattern 50). Next, the etching mask film 40 is wet etched using the resist film pattern 50 as a mask, and an etching mask film pattern 40a is formed on the pattern forming thin film 30 (see fig. 3 b), and a first etching mask film pattern 40a is formed in this step. Next, the pattern forming thin film 30 is wet etched using the etching mask film pattern 40a as a mask, and a pattern forming thin film pattern 30a is formed on the transparent substrate 20 (see fig. 3 (c), a process of forming the pattern forming thin film pattern 30 a). Thereafter, the process of forming the second resist film pattern 60 and the process of forming the second etching mask film pattern 40b may be included (see fig. 3 d and 3 e).
More specifically, in the step of forming the first resist film pattern 50, first, a resist film is formed on the etching mask film 40 of the mask blank 10 of the present embodiment shown in fig. 1. The resist film material used is not particularly limited. The resist film may be exposed to a laser beam having any wavelength selected from the wavelength range of 350nm to 436nm described later. The resist film may be either positive or negative.
Thereafter, a desired pattern is drawn on the resist film using a laser beam having an arbitrary wavelength selected from a wavelength region of 350nm to 436 nm. The pattern drawn on the resist film is a pattern formed on the thin film for pattern formation 30. The pattern drawn on the resist film may be a line and space pattern or a hole pattern.
Thereafter, as shown in fig. 3 (a), the resist film is developed with a predetermined developer, and a first resist film pattern 50 is formed on the etching mask film 40.
Formation process of first etching mask film pattern 40a
In the first etching mask film pattern 40a forming step, first, the etching mask film 40 is etched using the first resist film pattern 50 as a mask, thereby forming the first etching mask film pattern 40a. The etching mask film 40 may be formed of a chromium-based material containing chromium (Cr). In the case where the etching mask film 40 has a columnar structure, the etching rate is high, and side etching can be suppressed, which is preferable. The etching liquid for etching the etching mask film 40 is not particularly limited as long as the etching liquid can selectively etch the etching mask film 40. Specifically, an etching solution containing ammonium ceric nitrate and perchloric acid is exemplified.
Thereafter, as shown in fig. 3 (b), the first resist film pattern 50 is stripped using a resist stripping liquid, or by ashing. In some cases, the formation process of the next thin film pattern 30a for pattern formation may be performed without peeling the first resist film pattern 50.
Process for forming pattern 30a of thin film for pattern formation
As shown in fig. 3 (c), in the step of forming the first pattern forming thin film pattern 30a, the pattern forming thin film 30a is wet etched using the first etching mask film pattern 40a as a mask, thereby forming the pattern forming thin film pattern 30a. The pattern forming thin film pattern 30a may be a line pattern, a space pattern, or a hole pattern. The etching liquid for etching the thin film for pattern formation 30 is not particularly limited as long as the thin film for pattern formation 30 can be selectively etched. Examples thereof include an etching solution a (an etching solution containing ammonium bifluoride and hydrogen peroxide, etc.), and an etching solution B (an etching solution containing ammonium bifluoride, phosphoric acid, and hydrogen peroxide, etc.).
In order to make the cross-sectional shape of the pattern-forming thin film pattern 30a good, the wet etching is preferably performed for a longer time (overetching time) than the time (etching time only) for which the light-transmitting substrate 20 is exposed in the pattern-forming thin film pattern 30a. As the overetching time, when considering the influence on the light-transmitting substrate 20 or the like, it is preferable to increase the etching time by 20% of the etching time, more preferably by 10% of the etching time.
Process for forming second resist film pattern 60
In the second resist film pattern 60 forming step, first, a resist film is formed to cover the first etching mask film pattern 40 a. The resist film material used is not particularly limited. For example, the laser beam may be subjected to light having any wavelength selected from the wavelength range of 350nm to 436nm described later. The resist film may be either positive or negative.
Thereafter, a desired pattern is drawn on the resist film using a laser beam having an arbitrary wavelength selected from a wavelength region of 350nm to 436 nm. The pattern drawn on the resist film is a light shielding band pattern shielding the outer peripheral region of the region where the pattern forming thin film pattern 30a is formed, a light shielding band pattern shielding the central portion of the pattern forming thin film pattern 30a, and the like. The pattern drawn on the resist film may be a pattern having no light shielding band pattern for shielding the central portion of the pattern forming thin film pattern 30a, depending on the transmittance of the pattern forming thin film 30 with respect to the exposure light.
Thereafter, as shown in fig. 3 (d), the resist film is developed with a predetermined developer, and a second resist film pattern 60 is formed on the first etching mask film pattern 40 a.
Formation process of second etching mask film pattern 40b
As shown in fig. 3 (e), in the step of forming the second etching mask film pattern 40b, the first etching mask film pattern 40a is etched using the second resist film pattern 60 as a mask, thereby forming the second etching mask film pattern 40b. The first etching mask film pattern 40a may be formed of a chromium-based material containing chromium (Cr). The etching liquid for etching the first etching mask film pattern 40a is not particularly limited as long as the etching liquid can selectively etch the first etching mask film pattern 40 a. For example, an etching solution containing ammonium ceric nitrate and perchloric acid can be exemplified.
Thereafter, the second resist film pattern 60 is stripped using a resist stripping liquid or by ashing.
Thus, the transfer mask 100 can be obtained. That is, the transfer pattern included in the transfer mask 100 of the present embodiment may include the pattern forming thin film pattern 30a and the second etching mask film pattern 40b.
In the above description, the etching mask film 40 has been described as having a function of blocking transmission of exposure light. In the above description, the second resist film pattern 60 and the second etching mask film pattern 40b are not formed in the case where the etching mask film 40 simply has the function of a hard mask when the thin film 30 for forming a pattern is etched. In this case, after the step of forming the pattern forming thin film pattern 30a, the first etching mask film pattern 40a is peeled off, and the transfer mask 100 is manufactured. That is, the transfer pattern included in the transfer mask 100 may be constituted only by the pattern forming thin film pattern 30 a.
According to the method for manufacturing the transfer mask 100 of the present embodiment, the etching time can be shortened and the thin film pattern 30a for forming a pattern having a good cross-sectional shape can be formed by using the mask blank 10 shown in fig. 1. Therefore, the transfer mask 100 in which the transfer pattern including the high-definition pattern forming thin film pattern 30a can be transferred with high accuracy can be manufactured. The transfer mask 100 thus manufactured can be adapted to the refinement of the line and space pattern and/or the contact hole.
Method for manufacturing transfer mask 100 shown in FIG. 4
The method for manufacturing the transfer mask 100 shown in fig. 4 is a method for manufacturing the transfer mask 100 using the mask blank 10 shown in fig. 2. The method for manufacturing the transfer mask 100 shown in fig. 4 includes: a step of preparing a mask blank 10 shown in fig. 2; and a step of forming a resist film on the pattern forming film 30, and wet etching the pattern forming film 30 using the resist film pattern formed by the resist film as a mask to form a transfer pattern on the transparent substrate 20.
Specifically, in the method for manufacturing the transfer mask 100 shown in fig. 4, a resist film is formed on the mask blank 10. Next, a resist film pattern 50 is formed by performing patterning and development of a desired pattern on the resist film (fig. 4 (a), a process of forming the first resist film pattern 50). Next, the pattern forming thin film 30 is wet etched using the resist film pattern 50 as a mask, and a pattern forming thin film pattern 30a is formed on the transparent substrate 20 (fig. 4 (b) and (c), a process of forming the pattern forming thin film pattern 30 a).
More specifically, in the resist film pattern forming step, first, a resist film is formed on the thin film 30 for pattern formation of the mask blank 10 of the present embodiment shown in fig. 2. The resist film material used is the same as that described above. Before forming the resist film as needed, the surface modification treatment may be performed on the thin film for pattern formation 30 in order to improve the close contact property between the thin film for pattern formation 30 and the resist film. As described above, after forming the resist film, a desired pattern is drawn on the resist film using a laser beam having an arbitrary wavelength selected from a wavelength region of 350nm to 436 nm. Thereafter, as shown in fig. 4 (a), the resist film is developed with a predetermined developer, and a resist film pattern 50 is formed on the thin film for pattern formation 30.
Process for forming pattern 30a of thin film for pattern formation
As shown in fig. 4 (b), in the step of forming the pattern forming thin film pattern 30a, the pattern forming thin film 30 is etched using the resist film pattern as a mask, thereby forming the pattern forming thin film pattern 30a. The etching solution and the overetching time for etching the pattern forming thin film pattern 30a and the pattern forming thin film 30 are the same as those described in the embodiment shown in fig. 3.
Thereafter, the resist film pattern 50 is stripped using a resist stripping liquid or by ashing (fig. 4 (c)).
In this way, the transfer mask 100 can be obtained. The transfer pattern included in the transfer mask 100 of the present embodiment is constituted only by the pattern forming thin film pattern 30a, but other film patterns may be included. Examples of the other film include a film for suppressing reflection and a conductive film.
According to the method for manufacturing the transfer mask 100 of this embodiment, since the mask blank 10 shown in fig. 2 is used, the transmittance of the transparent substrate 20 is not reduced by the damage of the wet etching liquid to the transparent substrate, the etching time can be shortened, and the pattern forming thin film pattern 30a having a good cross-sectional shape can be formed. Therefore, the transfer mask 100 in which the transfer pattern including the high-definition pattern forming thin film pattern 30a can be transferred with high accuracy can be manufactured. The transfer mask 100 thus manufactured can be adapted to the refinement of the line and space pattern and/or the contact hole.
Method for manufacturing display device
A method for manufacturing a display device according to this embodiment will be described. The method for manufacturing a display device according to the present embodiment includes an exposure step of placing the transfer mask 100 according to the present embodiment on a mask stage of an exposure device, and exposing and transferring a transfer pattern formed on the transfer mask 100 for manufacturing a display device to a resist formed on a substrate for a display device.
Specifically, the method for manufacturing a display device according to the present embodiment includes: a step of placing the transfer mask 100 manufactured using the mask blank 10 on a mask stage of an exposure apparatus (mask placement step), and a step of exposing and transferring a transfer pattern to a resist film on a substrate for a display apparatus (exposure step). The following describes each step in detail.
Mounting Process
In the mounting step, the transfer mask 100 according to the present embodiment is mounted on a mask stage of an exposure apparatus. Here, the transfer mask 100 is disposed to face a resist film formed on a display device substrate via a projection optical system of an exposure apparatus.
Pattern transfer process
In the pattern transfer step, exposure light is irradiated to the transfer mask 100, and a resist film formed on the display device substrate transfers a transfer pattern including the pattern forming thin film pattern 30 a. The exposure light is a composite light including light having a plurality of wavelengths selected from a wavelength range of 313nm to 436nm, or monochromatic light selected from a wavelength range of 313nm to 436nm by cutting a certain wavelength range by a filter or the like, or monochromatic light emitted from a light source having a wavelength range of 313nm to 436 nm. For example, the exposure light is a composite light including at least one of i-line, h-line, and g-line, or a monochromatic light of i-line. By using the composite light as the exposure light, the exposure light intensity can be increased, thereby improving the throughput. Therefore, the manufacturing cost of the display device can be reduced.
According to the method for manufacturing a display device of the present embodiment, a high-definition display device having a high resolution and a fine line and space pattern and/or contact hole can be manufactured.
In the above embodiment, the case where the mask blank 10 having the pattern forming film 30 and the transfer mask 100 having the pattern forming film pattern 30a are used will be described. The pattern forming thin film 30 may be, for example, a phase shift film having a phase shift effect, or a light shielding film. Therefore, the transfer mask 100 of the present embodiment includes a phase shift mask having a phase shift film pattern and a binary mask having a light shielding film pattern. The mask blank 10 of the present embodiment includes a phase shift mask blank and a binary mask blank which are raw materials of the phase shift mask and the binary mask.
Examples (example)
The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.
(first embodiment)
To manufacture the mask blank 10 of the first embodiment, first, as the light-transmitting substrate 20, a synthetic quartz glass substrate of 1214 size (1220 mm×1400 mm) was prepared.
Thereafter, the synthetic quartz glass substrate is mounted on a tray (not shown) with its main surface facing downward, and is fed into a chamber of the continuous sputtering apparatus.
In order to form the thin film 30 for patterning on the main surface of the light-transmitting substrate 20, first, argon (Ar) gas and nitrogen (N) gas are introduced into the first chamber 2 ) A mixed gas of gases. Then, using a first sputtering target (titanium: silicon=5:7) containing titanium and silicon, a nitride of titanium silicide containing titanium, silicon, and nitrogen was laminated on the main surface of the light-transmitting substrate 20 by reactive sputtering. Thus, a thin film 30 for pattern formation (Ti: si: N: o=20.4:26.7:51.3:1.6 atomic%) made of titanium silicide nitride and having a film thickness of 115nm was formed. Here, the composition of the thin film 30 for pattern formation is a result obtained by measurement based on X-ray photoelectron spectroscopy (XPS). The measurement method of the film composition was also the same for other films (the same also applies to the second to fourth examples and the first and second comparative examples). The pattern forming thin film 30 is a phase shift film having a phase shift effect.
Then, the light-transmitting substrate 20 with the pattern-forming film 30 is fed into the second chamber, and argon (Ar) gas and nitrogen (N) gas are introduced into the second chamber 2 ) A mixed gas of gases. Then, using a second sputtering target formed of chromium, chromium nitride (CrN) containing chromium and nitrogen is formed on the thin film for pattern formation 30 by reactive sputtering. Next, a mixed gas of argon (Ar) gas and methane (CH 4) gas was introduced into the third chamber in a state in which the third chamber was set to a predetermined vacuum degree, and chromium carbide (CrC) containing chromium and carbon was formed on CrN by reactive sputtering using a third sputtering target formed of chromium. Finally, argon (Ar) gas and methane (CH) are introduced into the fourth chamber with a predetermined vacuum degree 4 ) Mixed gas of gases and nitrogen (N) 2 ) Gas and oxygen (O) 2 ) The mixed gas of gases forms chromium carbonitride (CrCON) containing chromium, carbon, oxygen and nitrogen on CrC by reactive sputtering using a fourth sputtering target formed of chromium. As described above, the laminated structure of the CrN layer, the CrC layer, and the CrCON layer is formed on the pattern forming film 30Is provided for the etching mask film 40.
Thus, the mask blank 10 in which the pattern forming thin film 30 and the etching mask film 40 were formed on the light-transmitting substrate 20 was obtained.
The thin film for patterning of the first example was formed on the main surface of another synthetic quartz substrate (about 152 mm. Times.152 mm), and another thin film for patterning was formed under the same conditions as those of the first example. Next, X-ray photoelectron spectroscopy analysis was performed on the pattern forming film on the other synthetic quartz substrate. In the X-ray photoelectron spectroscopy, the intensity of photoelectrons released from a thin film for pattern formation was measured by irradiating an inner region of the thin film for pattern formation with X-rays (AlK. Alpha. Line: 1486 eV), and sputtering with Ar gas at a voltage of 2.0kV and about 5 nm/min (SiO 2 Converted), the inner region of the thin film for patterning was excavated at the sputtering rate, the intensity of photoelectrons released from the excavated region was measured by irradiating the inner region with X-rays, and the above steps were repeated to obtain Ti2p narrow spectra of each depth of the inner region of the thin film for patterning (the same applies to the second to fourth examples, the first and second comparative examples, and so forth).
Fig. 5 is a graph showing the results (Ti 2p narrow spectrum) of X-ray photoelectron spectroscopy analysis performed on the patterning thin films on the other synthetic quartz substrates according to the respective embodiments of the present invention. FIG. 6 is a graph showing the result (Si 2p narrow spectrum) of X-ray photoelectron spectroscopy analysis with respect to the phase shift film of the mask blank according to each example of the present invention. Each of the narrow spectra shown in fig. 5 and 6 was obtained at a depth position (depth position substantially at the center in the film thickness direction of the inner region) defined by the thin film for pattern formation on the other synthetic quartz substrate of each example. As determined from the values shown in FIGS. 5 and 6, in the narrow spectrum of Ti2P and the narrow spectrum of Si2P of the first embodiment, P N /P S 1.84, satisfies a relation greater than 1.18 (as described above, the photoelectron intensity of which is made 455eV to be P N The photoelectron intensity of 102eV is set to be P S . The same applies below).
In addition, atThe narrow spectrum of Ti2P, the narrow spectrum of Si2P of the first embodiment, P NU /P S 1.60, satisfies a relation greater than 1.05 (as described above, the photoelectron intensity of 461eV is made P NU . The same applies below).
In addition, in the narrow spectrum of Ti2P and the narrow spectrum of Si2P of the first embodiment, (P N +P NU )/P S A relationship greater than 2.22 is satisfied for 3.44.
In addition, in the narrow spectrum of Ti2P of the first embodiment, P N /P TS Is 3.06, satisfies a relation greater than 2.13 (the photoelectron intensity at which the binding energy is 453eV is made to be P as described above TS . The same applies below).
In addition, in the narrow spectrum of Ti2P of the first embodiment, (P N +P T )/P TS A relationship greater than 3.53 is satisfied at 4.62.
In the first embodiment, the above ratios are also satisfied for each of the Ti2p narrow spectra and each of the Si2p narrow spectra at other depth positions in the internal region.
Transmittance and phase difference measurement
The transmittance (wavelength: 365 nm) and the retardation (wavelength: 365 nm) of the surface of the pattern forming film 30 of the mask blank 10 of the first example were measured using MPM-100 manufactured by LaserTech corporation (U.S.). The transmittance and the retardation of the patterning thin film 30 were measured using a substrate with a thin film obtained by forming another patterning thin film on the main surface of the other synthetic quartz glass substrate (the same applies to the second, third, and fourth examples and the first and second comparative examples). As a result, the film 30 for pattern formation of the first embodiment had a transmittance of 6% and a phase difference of 180 degrees.
Transfer mask 100 and method for manufacturing the same
Using the mask blank 10 of the first embodiment manufactured as described above, a transfer mask 100 was manufactured. First, a photoresist film is coated on the etching mask film 40 of the mask blank 10 using a resist coating apparatus.
After that, a photoresist film is formed through a heating/cooling process.
Thereafter, the photoresist film was drawn by using a laser drawing apparatus, and a resist film pattern having a hole pattern with a hole diameter of 1.5 μm was formed on the etching mask film 40 through a developing/rinsing process.
Thereafter, the etching mask film 40 is wet etched using a chromium etching solution containing ceric ammonium nitrate and perchloric acid with the resist film pattern as a mask, thereby forming a first etching mask film pattern 40a.
Thereafter, the pattern forming thin film 30 is wet etched using the titanium silicide etching solution diluted with the mixture solution of ammonium bifluoride and hydrogen peroxide using the first etching mask film pattern 40a as a mask, thereby forming the pattern forming thin film pattern 30a.
After that, the resist film pattern is peeled off.
Thereafter, a photoresist film is coated to cover the first etching mask film pattern 40a using a resist coating apparatus.
After that, a photoresist film is formed through a heating/cooling process.
Thereafter, the photoresist film is drawn using a laser drawing apparatus, and a second resist film pattern 60 for forming a light shielding tape is formed on the first etching mask film pattern 40a through a developing/rinsing process.
Thereafter, the first etching mask film pattern 40a formed in the transfer pattern formation region is wet etched using a chromium etching solution containing ceric ammonium nitrate and perchloric acid with the second resist film pattern 60 as a mask.
After that, the second resist film pattern 60 is peeled off.
In this way, the transfer mask 100 of the first embodiment in which the pattern forming thin film pattern 30a having an aperture of 1.5 μm and the light shielding tape formed of the laminated structure of the pattern forming thin film pattern 30a and the etching mask film pattern 40b were formed on the light transmitting substrate 20 was obtained.
Cross-sectional shape of transfer mask 100
The cross section of the transfer mask 100 thus obtained was observed by a scanning electron microscope.
The pattern forming thin film pattern 30a of the transfer mask 100 of the first embodiment has a cross-sectional shape close to vertical. Therefore, the pattern forming thin film pattern 30a formed on the transfer mask 100 according to the first embodiment has a cross-sectional shape capable of sufficiently exhibiting the phase shift effect.
As described above, it can be said that when the transfer mask 100 of the first embodiment is placed on the mask stage of the exposure apparatus, and the resist film on the display device substrate is exposed and transferred, the transfer pattern including the fine pattern smaller than 2.0 μm can be transferred with high accuracy.
Light resistance/drug resistance
A sample in which the thin film 30 for pattern formation used in the mask blank 10 of the first embodiment was formed on the light-transmitting substrate 20 was prepared. The total irradiation amount was set to 10kJ/cm with respect to the pattern forming film 30 of the sample of the first embodiment 2 Light of a metal halide light source including ultraviolet rays having a wavelength of 365nm is irradiated. The transmittance was measured before and after the predetermined ultraviolet irradiation, and the change in the transmittance [ (transmittance after the ultraviolet irradiation) - (transmittance before the ultraviolet irradiation) was calculated]Thus, the light resistance of the film for pattern formation 30 was evaluated. The transmittance was measured using a spectrophotometer.
In the first example, the change in transmittance before and after ultraviolet irradiation was 0.09% (0.09 point). As is clear from the above description, the film for pattern formation of the first embodiment is a film having sufficiently high light resistance in practical use.
A sample in which the thin film 30 for pattern formation used in the mask blank 10 of the first embodiment was formed on the light-transmitting substrate 20 was prepared. With respect to the thin film for pattern formation 30 of the sample of the first example, five cycles of cleaning test were performed as one cycle with SPM cleaning (cleaning time: 5 minutes) with a mixed solution of sulfuric acid and hydrogen peroxide and SC-1 cleaning (cleaning time: 5 minutes) with a mixed solution of ammonia, hydrogen peroxide and water, and the chemical resistance of the thin film for pattern formation 30 was evaluated.
The reflectance spectra in the wavelength range of 200nm to 500nm before and after the cleaning test were measured, and the chemical resistance of the thin film for pattern formation 30 was evaluated based on the amount of change in the wavelength (bottom peak wavelength) corresponding to the lowest reflectance in which the reflectance was projected downward.
As a result of the drug resistance evaluation, in the first example having the thin film for forming a titanium silicide pattern, the variation of the bottom peak wavelength per cleaning cycle was smaller by 1.0nm or less toward the short wavelength side, and the drug resistance was good.
As is clear from this, the film for patterning of the first embodiment is an unprecedented good film that satisfies desired optical characteristics (transmittance, retardation), and has both high light resistance (drug resistance), high etching rate, and good cross-sectional shape.
(second embodiment)
The mask blank 10 of the second embodiment is manufactured in the same procedure as the mask blank 10 of the first embodiment except that the film 30 for pattern formation is as described below.
The method of forming the pattern forming film 30 of the second embodiment is as follows.
In order to form the thin film 30 for patterning on the main surface of the light-transmitting substrate 20, first, a gas consisting of argon (Ar) and nitrogen (N) is introduced into the first chamber 2 ) A mixed gas of gases. Then, using a first sputtering target (titanium: silicon=1:2) containing titanium and silicon, a nitride of titanium silicide containing titanium, silicon, and nitrogen was laminated on the main surface of the light-transmitting substrate 20 by reactive sputtering. Thus, a thin film 30 for pattern formation (Ti: si: N: o=15.4:31.6:50.9:2.1 atomic%) made of titanium silicide nitride and having a film thickness of 130nm was formed.
Thereafter, the etching mask film 40 is formed in the same manner as in the first embodiment.
Then, other thin films for pattern formation were formed on the main surfaces of other synthetic quartz substrates under the same film formation conditions as in the second embodiment. Next, with respect to the pattern forming film on the other synthetic quartz substrate, X-ray photoelectron spectroscopy analysis was performed in the same manner as in the first embodiment.
As determined from the values shown in FIGS. 5 and 6, in the narrow spectrum of Ti2P and the narrow spectrum of Si2P of the second embodiment, P N /P S 1.36, satisfying a relationship greater than 1.18.
In addition, in the narrow spectrum of Ti2P and the narrow spectrum of Si2P of the second embodiment, P NU /P S A relationship greater than 1.05 is satisfied for 1.23.
In addition, in the narrow spectrum of Ti2P and the narrow spectrum of Si2P of the second embodiment, (P N +P NU )/P S A relationship greater than 2.22 is satisfied for 2.59.
In addition, in the narrow spectrum of Ti2P of the second embodiment, P N /P TS A relationship greater than 2.13 is satisfied for 2.53.
In addition, in the narrow spectrum of Ti2P of the second embodiment, (P N +P T )/P TS A relationship greater than 3.53 is satisfied for 3.96.
In the second embodiment, the above ratios are also satisfied for each of the Ti2p narrow spectra and each of the Si2p narrow spectra at other depth positions in the internal region.
Transmittance and phase difference measurement
The transmittance (wavelength: 365 nm) and the retardation (wavelength: 365 nm) of the surface of the pattern forming film 30 of the mask blank 10 of the second example were measured by using MPM-100 manufactured by LaserTech corporation (U.S.A.). As a result, the film 30 for pattern formation of the second embodiment had a transmittance of 14% and a phase difference of 180 degrees.
Transfer mask 100 and method for manufacturing the same
Using the mask blank 10 of the second embodiment manufactured as described above, the transfer mask 100 was manufactured in the same flow as the first embodiment, and the transfer mask 100 of the second embodiment in which the pattern forming thin film pattern 30a having an aperture of 1.5 μm and the light shielding tape formed of the laminated structure of the pattern forming thin film pattern 30a and the etching mask film pattern 40b were formed on the light-transmitting substrate 20 was obtained.
Cross-sectional shape of transfer mask 100
The cross section of the transfer mask 100 thus obtained was observed by a scanning electron microscope.
The pattern forming thin film pattern 30a of the transfer mask 100 of the second embodiment has a cross-sectional shape close to vertical. Therefore, the pattern forming thin film pattern 30a formed on the transfer mask 100 according to the second embodiment has a cross-sectional shape capable of sufficiently exhibiting the phase shift effect.
As described above, it can be said that when the transfer mask 100 of the second embodiment is placed on the mask stage of the exposure apparatus, and the resist film on the display device substrate is exposed and transferred, the transfer pattern including the fine pattern smaller than 2.0 μm can be transferred with high accuracy.
Light resistance/drug resistance
A sample in which the thin film 30 for pattern formation used in the mask blank 10 of the second embodiment was formed on the light-transmitting substrate 20 was prepared. The total irradiation amount was set to 10kJ/cm with respect to the pattern forming film 30 of the sample of the second embodiment 2 Light of a metal halide light source including ultraviolet rays having a wavelength of 365nm is irradiated. The transmittance was measured before and after the predetermined ultraviolet irradiation, and the change in the transmittance [ (transmittance after the ultraviolet irradiation) - (transmittance before the ultraviolet irradiation) was calculated]The light resistance of the film for pattern formation 30 was thereby evaluated. The transmittance was measured using a spectrophotometer.
In the second example, the change in transmittance before and after ultraviolet irradiation was 0.34% (0.34 point). As is clear from the above description, the film for pattern formation of the second embodiment is a film having sufficiently high light resistance in practical use.
In addition, a sample in which the thin film 30 for pattern formation used in the mask blank 10 of the second embodiment was formed on the light-transmitting substrate 20 was prepared, and the resistance of the thin film 30 for pattern formation was evaluated in the same manner as in the first embodiment.
As a result of the drug resistance evaluation, in the second example having the thin film for forming a titanium silicide pattern, the variation of the bottom peak wavelength per cleaning cycle was smaller by 1.0nm or less toward the short wavelength side, and the drug resistance was good.
As is clear from this, the film for pattern formation according to the second embodiment is an unprecedented good film that satisfies desired optical characteristics (transmittance and retardation), and has high light resistance (chemical resistance), high etching rate, and good cross-sectional shape.
(third embodiment)
The mask blank 10 of the third embodiment is manufactured in the same procedure as the mask blank 10 of the first embodiment except that the film 30 for pattern formation is as described below.
The method of forming the pattern forming film 30 of the third embodiment is as follows.
In order to form the thin film 30 for patterning on the main surface of the light-transmitting substrate 20, first, a gas consisting of argon (Ar) and nitrogen (N) is introduced into the first chamber 2 ) A mixed gas of gases. Then, using a first sputtering target (titanium: silicon=1:3) containing titanium and silicon, a nitride of titanium silicide containing titanium, silicon, and nitrogen was laminated on the main surface of the light-transmitting substrate 20 by reactive sputtering. Thus, a thin film 30 for pattern formation (Ti: si: N: o=11.4:35.4:52.4:0.8 atomic%) made of titanium silicide nitride and having a film thickness of 131nm was formed.
Thereafter, the etching mask film 40 is formed in the same manner as in the first embodiment.
Then, other thin films for pattern formation were formed on the main surfaces of other synthetic quartz substrates under the same film formation conditions as in the above-described third embodiment. Next, with respect to the pattern forming film on the other synthetic quartz substrate, X-ray photoelectron spectroscopy analysis was performed in the same manner as in the first embodiment.
As determined from the values shown in FIGS. 5 and 6, in the narrow spectrum of Ti2P and the narrow spectrum of Si2P of the third embodiment, P N /P S 1.25, satisfying a relationship greater than 1.18.
In addition, in the narrow spectrum of Ti2P and the narrow spectrum of Si2P of the third embodiment, P NU /P S 1.18, satisfying a relationship greater than 1.05.
In addition, in the narrow spectrum of Ti2P and the narrow spectrum of Si2P of the third embodiment, (P N +P NU )/P S A relationship greater than 2.22 is satisfied for 2.43.
In the third embodiment, the above ratios are satisfied for each of the Ti2p narrow spectra and each of the Si2p narrow spectra at other depth positions in the internal region.
Transmittance and phase difference measurement
The transmittance (wavelength: 365 nm) and the retardation (wavelength: 365 nm) of the surface of the pattern forming film 30 of the mask blank 10 of the third example were measured by using MPM-100 manufactured by LaserTech corporation (U.S.A.). As a result, the film 30 for pattern formation of the third example had a transmittance of 18% and a phase difference of 180 degrees.
Transfer mask 100 and method for manufacturing the same
Using the mask blank 10 of the third embodiment manufactured as described above, the transfer mask 100 of the third embodiment in which the pattern forming thin film pattern 30a having an aperture of 1.5 μm and the light shielding tape formed of the laminated structure of the pattern forming thin film pattern 30a and the etching mask film pattern 40b were formed on the light-transmitting substrate 20 was obtained by manufacturing the transfer mask 100 in the same flow as the first embodiment.
Cross-sectional shape of transfer mask 100
The cross section of the transfer mask 100 thus obtained was observed by a scanning electron microscope.
The pattern forming thin film pattern 30a of the transfer mask 100 of the third embodiment has a cross-sectional shape close to vertical. Therefore, the pattern forming thin film pattern 30a formed on the transfer mask 100 according to the third embodiment has a cross-sectional shape capable of sufficiently exhibiting the phase shift effect.
From the above description, it can be said that when the transfer mask 100 of the third embodiment is placed on the mask stage of an exposure apparatus, and the resist film on the substrate for a display apparatus is exposed and transferred, a transfer pattern including a fine pattern smaller than 2.0 μm can be transferred with high accuracy.
Light resistance/drug resistance
Is prepared on a light-transmitting substrateA sample of the film 30 for pattern formation used in the mask blank 10 of the third embodiment was formed on 20. The total irradiation amount was set to 10kJ/cm with respect to the pattern forming film 30 of the sample of the third embodiment 2 Light of a metal halide light source including ultraviolet rays having a wavelength of 365nm is irradiated. The transmittance was measured before and after the predetermined ultraviolet irradiation, and the change in the transmittance [ (transmittance after the ultraviolet irradiation) - (transmittance before the ultraviolet irradiation) was calculated ]The light resistance of the film 30 for pattern formation was thereby evaluated. The transmittance was measured using a spectrophotometer.
In the third example, the change in transmittance before and after ultraviolet irradiation was 0.45% (0.45 point). As is clear from the above description, the film for pattern formation of the third embodiment is a film having sufficiently high light resistance in practical use.
In addition, a sample in which the thin film 30 for pattern formation used in the mask blank 10 of the third embodiment was formed on the light-transmitting substrate 20 was prepared, and the resistance of the thin film 30 for pattern formation was evaluated in the same manner as in the first embodiment.
As a result of the drug resistance evaluation, in the third example having the titanium silicide-based thin film for pattern formation, the variation of the bottom peak wavelength per cleaning cycle was smaller by 1.0nm or less toward the short wavelength side, and the drug resistance was good.
As is clear from this, the film for pattern formation according to the third example is an unprecedented good film having desired optical characteristics (transmittance and retardation), high light resistance (chemical resistance), high etching rate, and good cross-sectional shape.
(fourth embodiment)
The mask blank 10 of the fourth embodiment is manufactured in the same procedure as the mask blank 10 of the first embodiment except that the thin film 30 for pattern formation is as described below.
The method of forming the pattern forming film 30 of the fourth embodiment is as follows.
In order to form the thin film 30 for patterning on the main surface of the light-transmitting substrate 20, first, a gas consisting of argon (Ar) and nitrogen (N) is introduced into the first chamber 2 ) Air flowAnd (3) forming a mixed gas. Then, using a first sputtering target (titanium: silicon=1:3) containing titanium and silicon, a nitride of titanium silicide containing titanium, silicon, and nitrogen was laminated on the main surface of the light-transmitting substrate 20 by reactive sputtering. Thus, a thin film 30 for pattern formation (Ti: si: N: o=11.7:35.0:52.0:1.3 atomic%) made of titanium silicide nitride and having a film thickness of 134nm was formed.
Thereafter, the etching mask film 40 is formed in the same manner as in the first embodiment.
Then, under the same film forming conditions as in the fourth embodiment, other thin films for pattern formation and etching mask films were formed on the main surfaces of the other light-transmitting substrates, respectively. Next, with respect to the pattern forming film on the other light-transmitting substrate, X-ray photoelectron spectroscopy was performed in the same manner as in the first embodiment.
As determined from the values shown in FIGS. 5 and 6, in the narrow spectrum of Ti2P and the narrow spectrum of Si2P of the fourth embodiment, P N /P S 1.19, satisfying a relationship greater than 1.18.
In addition, in the narrow spectrum of Ti2P and the narrow spectrum of Si2P of the fourth embodiment, P NU /P S 1.11, satisfies a relationship greater than 1.05.
In addition, in the narrow spectrum of Ti2P and the narrow spectrum of Si2P of the fourth embodiment, (P) N +P NU )/P S A relationship greater than 2.22 is satisfied for 2.30.
In the fourth embodiment, the above ratios are satisfied for each of the Ti2p narrow spectra and each of the Si2p narrow spectra at other depth positions in the internal region.
Transmittance and phase difference measurement
The transmittance (wavelength: 365 nm) and the retardation (wavelength: 365 nm) of the surface of the pattern forming film 30 of the mask blank 10 of the fourth example were measured by using MPM-100 manufactured by LaserTech corporation (U.S.A.). As a result, the film 30 for pattern formation of the fourth example had a transmittance of 22% and a phase difference of 180 degrees.
Transfer mask 100 and method for manufacturing the same
Using the mask blank 10 of the fourth embodiment manufactured as described above, the transfer mask 100 of the fourth embodiment in which the pattern forming thin film pattern 30a having an aperture of 1.5 μm and the light shielding tape formed of the laminated structure of the pattern forming thin film pattern 30a and the etching mask film pattern 40b were formed on the light-transmitting substrate 20 was obtained by manufacturing the transfer mask 100 in the same flow as the first embodiment.
Cross-sectional shape of transfer mask 100
The cross section of the transfer mask 100 thus obtained was observed by a scanning electron microscope.
The pattern forming thin film pattern 30a of the transfer mask 100 of the fourth embodiment has a cross-sectional shape close to vertical. Therefore, the pattern forming thin film pattern 30a formed on the transfer mask 100 according to the fourth embodiment has a cross-sectional shape capable of sufficiently exhibiting the phase shift effect.
From the above description, it can be said that when the transfer mask 100 of the fourth embodiment is placed on the mask stage of an exposure apparatus, and the resist film on the substrate for a display apparatus is exposed and transferred, a transfer pattern including a fine pattern smaller than 2.0 μm can be transferred with high accuracy.
Light resistance/drug resistance
A sample in which the thin film 30 for pattern formation used in the mask blank 10 of the fourth embodiment was formed on the light-transmitting substrate 20 was prepared. The total irradiation amount was set to 10kJ/cm with respect to the pattern forming film 30 of the sample of the fourth embodiment 2 Light of a metal halide light source including ultraviolet rays having a wavelength of 365nm is irradiated. The transmittance was measured before and after the predetermined ultraviolet irradiation, and the change in the transmittance [ (transmittance after the ultraviolet irradiation) - (transmittance before the ultraviolet irradiation) was calculated ]The light resistance of the film 30 for pattern formation was thereby evaluated. The transmittance was measured using a spectrophotometer.
In the fourth example, the change in transmittance before and after ultraviolet irradiation was good, and was 1.48% (0.34 point). As is clear from the above description, the film for pattern formation of the fourth embodiment is a film having sufficiently high light resistance in practical use.
In addition, a sample in which the thin film 30 for pattern formation used in the mask blank 10 of the fourth embodiment was formed on the light-transmitting substrate 20 was prepared, and the resistance of the thin film 30 for pattern formation was evaluated in the same manner as in the first embodiment.
As a result of the drug resistance evaluation, in the fourth example having the titanium silicide-based thin film for pattern formation, the variation of the bottom peak wavelength per cleaning cycle was smaller by 1.0nm or less toward the short wavelength side, and the drug resistance was good.
As is clear from this, the film for pattern formation according to the fourth embodiment is an unprecedented good film that satisfies desired optical characteristics (transmittance and retardation), and has high light resistance (chemical resistance), high etching rate, and good cross-sectional shape.
(first comparative example)
The mask blank 10 of the first comparative example was manufactured in the same procedure as the mask blank 10 of the first embodiment except that the film 30 for pattern formation was as described below.
The method of forming the pattern forming film 30 of the first comparative example is as follows.
In order to form the thin film 30 for patterning on the main surface of the light-transmitting substrate 20, first, a gas consisting of argon (Ar) and nitrogen (N) is introduced into the first chamber 2 ) A mixed gas of gases. Then, using a first sputtering target (titanium: silicon=1:3) containing titanium and silicon, a nitride of titanium silicide containing titanium, silicon, and nitrogen was laminated on the main surface of the light-transmitting substrate 20 by reactive sputtering. Thus, a thin film 30 for pattern formation (Ti: si: N: o=11.7:35.5:51.0:1.8 atomic%) made of titanium silicide nitride and having a film thickness of 130nm was formed.
Thereafter, the etching mask film 40 is formed in the same manner as in the first embodiment.
Then, other patterning films were formed on the main surfaces of other synthetic quartz substrates under the same film formation conditions as in the first comparative example. Next, with respect to the pattern forming film on the other synthetic quartz substrate, X-ray photoelectron spectroscopy analysis was performed in the same manner as in the first embodiment.
FIG. 7 is a graph showing the results (Ti 2p narrow spectrum) of X-ray photoelectron spectroscopy analysis performed on the phase shift film of the mask blank of each comparative example of the present invention. FIG. 8 is a graph showing the results (Si 2p narrow spectrum) of X-ray photoelectron spectroscopy analysis performed on the phase shift film of the mask blank of each comparative example of the present invention. Each of the narrow spectra shown in fig. 7 and 8 was obtained at a predetermined depth position (depth position substantially at the center in the film thickness direction of the inner region) of the thin film for pattern formation on the other synthetic quartz substrate of each comparative example. As determined from the values shown in fig. 7 and 8, P is found in the narrow spectrum of Ti2P and the narrow spectrum of Si2P of the first comparative example N /P S A relationship greater than 1.18 is not satisfied for 1.18.
In addition, in the narrow spectrum of Ti2P and the narrow spectrum of Si2P of the first comparative example, P NU /P S A value of 1.05 does not satisfy a relation larger than 1.05.
In addition, in the narrow spectrum of Ti2P and the narrow spectrum of Si2P of the first comparative example, (P) N +P NU )/P S A relationship greater than 2.22 is not satisfied for 2.22.
In addition, in the narrow spectrum of Ti2P of the first comparative example, P N /P TS A relationship greater than 2.13 is not satisfied for 2.13.
In addition, in the narrow spectrum of Ti2P of the first comparative example, (P) N +P T )/P TS A relationship greater than 3.53 is not satisfied for 3.53.
Transmittance and phase difference measurement
The transmittance (wavelength: 365 nm) and the retardation (wavelength: 365 nm) of the surface of the pattern forming film 30 of the mask blank 10 of the first comparative example were measured by using MPM-100 manufactured by LaserTech corporation (U.S.A.). As a result, the film 30 for pattern formation of the first comparative example had a transmittance of 23% and a phase difference of 180 degrees.
Transfer mask 100 and method for manufacturing the same
Using the mask blank 10 of the first comparative example manufactured as described above, the transfer mask 100 was manufactured in the same flow as the first example, and the transfer mask 100 of the first comparative example in which the pattern forming thin film pattern 30a having an aperture of 1.5 μm and the light shielding tape formed of the laminated structure of the pattern forming thin film pattern 30a and the etching mask film pattern 40b were formed on the light-transmitting substrate 20 was obtained.
Cross-sectional shape of transfer mask 100
The cross section of the transfer mask 100 thus obtained was observed by a scanning electron microscope.
The pattern forming thin film pattern 30a of the transfer mask 100 of the first comparative example has a cross-sectional shape close to vertical. Therefore, the pattern forming thin film pattern 30a formed on the transfer mask 100 of the first comparative example has a cross-sectional shape capable of sufficiently exhibiting the phase shift effect.
From the above description, it can be said that when the transfer mask 100 of the first comparative example is placed on the mask stage of the exposure apparatus and the resist film on the substrate for the display apparatus is exposed and transferred, the transfer pattern including the fine pattern smaller than 2.0 μm can be transferred with high accuracy.
Light resistance/drug resistance
A pattern forming film 30 used in the mask blank 10 of the first comparative example was prepared to be formed on the light-transmitting substrate 20. The total irradiation amount of the pattern forming film 30 was set to 10kJ/cm with respect to the sample of the first comparative example 2 Light of a metal halide light source including ultraviolet rays having a wavelength of 365nm is irradiated. The transmittance was measured before and after the predetermined ultraviolet irradiation, and the change in the transmittance [ (transmittance after the ultraviolet irradiation) - (transmittance before the ultraviolet irradiation) was calculated ]The light resistance of the film 30 for pattern formation was thereby evaluated. The transmittance was measured using a spectrophotometer.
In the first comparative example, the transmittance change before and after the ultraviolet irradiation was 2.00% (2.00 points), which was outside the allowable range. As is clear from the above description, the film for pattern formation of the first comparative example does not have sufficient light resistance in practical use.
In addition, a sample in which the thin film 30 for pattern formation used in the mask blank 10 of the first comparative example was formed on the light-transmitting substrate 20 was prepared, and the resistance of the thin film 30 for pattern formation was evaluated in the same manner as in the first embodiment.
As a result of the drug resistance evaluation, in the first comparative example having the thin film for forming a titanium silicide pattern, the variation of the bottom peak wavelength per cleaning cycle was 1.0nm or less toward the short wavelength side, and the drug resistance was sufficient.
Thus, the film for pattern formation of the first comparative example did not have sufficient performance in light resistance.
(second comparative example)
The mask blank 10 of the second comparative example was manufactured in the same procedure as the mask blank 10 of the first embodiment except that the film 30 for pattern formation was as described below.
The method of forming the pattern forming film 30 of the second comparative example is as follows.
In order to form the thin film 30 for patterning on the main surface of the light-transmitting substrate 20, first, a gas consisting of argon (Ar) and nitrogen (N) is introduced into the first chamber 2 ) A mixed gas of gases. Then, using a first sputtering target (titanium: silicon=1:4) containing titanium and silicon, a nitride of titanium silicide containing titanium, silicon, and nitrogen was laminated on the main surface of the light-transmitting substrate 20 by reactive sputtering. Thus, a thin film 30 for pattern formation (Ti: si: N: o=7.6:33.6:40.6:18.2 atomic%) made of titanium silicide nitride and having a film thickness of 186nm was formed. The oxygen content of the thin film 30 is not limited to the intentionally introduced oxygen component, but rather to residual moisture or adsorbed carried-in moisture in the film forming apparatus.
Thereafter, the etching mask film 40 is formed in the same manner as in the first embodiment.
Then, other patterning films were formed on the main surfaces of other synthetic quartz substrates under the same film formation conditions as in the second comparative example. Next, with respect to the pattern forming film on the other synthetic quartz substrate, X-ray photoelectron spectroscopy analysis was performed in the same manner as in the first embodiment.
As determined from the values shown in fig. 7 and 8, P is found in the narrow spectrum of Ti2P and the narrow spectrum of Si2P of the second comparative example N /P S At 0.31, a switch of greater than 1.18 is not satisfiedIs tied up.
In addition, in the narrow spectrum of Ti2P and the narrow spectrum of Si2P of the second comparative example, P NU /P S A relationship greater than 1.05 is not satisfied at 0.33.
In addition, in the narrow spectrum of Ti2P and the narrow spectrum of Si2P of the second comparative example, (P) N +P NU )/P S A relationship greater than 2.22 is not satisfied for 0.64.
In addition, in the narrow spectrum of Ti2P of the second comparative example, P N /P TS A relationship greater than 2.13 is not satisfied for 1.53.
In addition, in the narrow spectrum of Ti2P of the second comparative example, (P) N +P T )/P TS A relationship greater than 3.53 is not satisfied for 2.64.
Transmittance and phase difference measurement
The transmittance (wavelength: 365 nm) and the retardation (wavelength: 365 nm) of the surface of the pattern forming film 30 of the mask blank 10 of the second comparative example were measured by using MPM-100 manufactured by LaserTech corporation (U.S.A.). As a result, the transmittance of the pattern forming film 30 of the second comparative example was 57%, and the phase difference was 180 degrees.
Transfer mask 100 and method for manufacturing the same
Using the mask blank 10 of the second comparative example manufactured as described above, the transfer mask 100 was manufactured in the same flow as the first embodiment, and the transfer mask 100 of the second comparative example in which the pattern forming thin film pattern 30a having an aperture of 1.5 μm and the light shielding tape formed of the laminated structure of the pattern forming thin film pattern 30a and the etching mask film pattern 40b were formed on the light-transmitting substrate 20 was obtained.
Cross-sectional shape of transfer mask 100
The cross section of the transfer mask 100 thus obtained was observed by a scanning electron microscope.
The pattern forming thin film pattern 30a of the transfer mask 100 of the second comparative example has a cross-sectional shape that excessively etches the boundary portion with the transparent substrate 20. Therefore, the pattern forming thin film pattern 30a formed on the transfer mask 100 of the second comparative example is not a cross-sectional shape that can sufficiently exhibit the phase shift effect.
According to the above description, when the transfer mask 100 of the second comparative example is placed on the mask stage of an exposure apparatus, and the resist film on the substrate for a display apparatus is exposed and transferred, it is difficult to transfer the transfer pattern including the fine pattern smaller than 2.0 μm with high accuracy.
Light resistance/drug resistance
A sample in which the pattern forming thin film 30 used in the mask blank 10 of the second comparative example was formed on the light-transmitting substrate 20 was prepared. The total irradiation amount of the pattern forming film 30 was set to 10kJ/cm with respect to the sample of the second comparative example 2 Light of a metal halide light source including ultraviolet rays having a wavelength of 365nm is irradiated. The transmittance was measured before and after the predetermined ultraviolet irradiation, and the change in the transmittance [ (transmittance after the ultraviolet irradiation) - (transmittance before the ultraviolet irradiation) was calculated ]The light resistance of the film for pattern formation 30 was thereby evaluated. The transmittance was measured using a spectrophotometer.
In the second comparative example, the change in transmittance before and after ultraviolet irradiation was 2.55% (2.55 points), which was outside the allowable range. As is clear from the above description, the film for pattern formation of the second comparative example does not practically have sufficient light resistance.
In addition, a sample in which the thin film 30 for pattern formation used in the mask blank 10 of the second comparative example was formed on the light-transmitting substrate 20 was prepared, and the resistance of the thin film 30 for pattern formation was evaluated in the same manner as in the first embodiment.
As a result of the drug resistance evaluation, in the second comparative example having the titanium silicide-based thin film for pattern formation containing 8 atomic% or more of oxygen, the amount of change in the bottom peak wavelength per cleaning cycle was 1.0nm or more toward the short wavelength side, and the drug resistance was also insufficient.
Thus, the film for pattern formation of the second comparative example does not have sufficient performance in light resistance and drug resistance.
In the above-described embodiments, the example of the transfer mask 100 for manufacturing a display device and the mask blank 10 for manufacturing the transfer mask 100 for manufacturing a display device are described, but not limited thereto. The mask blank 10 and/or the transfer mask 100 of the present invention can be applied to manufacturing of semiconductor devices, MEMS, printing substrates, and the like. The present invention can also be applied to a binary mask blank having a light shielding film as the pattern forming thin film 30, and a binary mask having a light shielding film pattern.
In the above embodiment, the example in which the size of the light-transmitting substrate 20 is 1214 (1220 mm×1400mm×13 mm) was described, but the present invention is not limited thereto. In the case of the mask blank 10 for manufacturing a display device, a Large (Large Size) light-transmitting substrate 20 is used, and the length of one side of the main surface is 300mm or more in the Size of the light-transmitting substrate 20. The size of the light-transmitting substrate 20 used in the mask blank 10 for manufacturing a display device is, for example, 330mm×450mm or more and 2280mm×3130mm or less.
In the case of the mask blank 10 for manufacturing a semiconductor device, MEMS, or print substrate, a Small (Small Size) light-transmitting substrate 20 is used, and the length of one side of the light-transmitting substrate 20 is 9 inches or less in Size. The size of the light-transmitting substrate 20 used in the mask blank 10 for the above-described application is, for example, 63.1mm×63.1mm or more and 228.6mm×228.6mm or less. In general, as the light-transmitting substrate 20 used for the transfer mask 100 for semiconductor device manufacturing and MEMS manufacturing, 6025 size (152 mm×152 mm) or 5009 size (126.6 mm×126.6 mm) is used. In general, as the translucent substrate 20 used for the transfer mask 100 for manufacturing a print substrate, a 7012 size (177.4 mm×177.4 mm) or a 9012 size (228.6 mm×228.6 mm) is used.
Claims (21)
1. A mask blank having a light-transmitting substrate and a pattern-forming film provided on a main surface of the light-transmitting substrate, characterized in that,
the film contains titanium, silicon and nitrogen,
an photoelectron intensity P of 455eV as a binding energy in a narrow spectrum of Ti2P obtained by analyzing an inner region of the film by X-ray photoelectron spectroscopy N In Si2p narrow spectrumThe photoelectron intensity of 102eV is P S When meeting P N /P S A relationship greater than 1.18,
the inner region is a region of the film other than a vicinity region on the light-transmitting substrate side and a surface layer region on the opposite side of the light-transmitting substrate,
the nitrogen content in the internal region is 30 atomic% or more.
2. The mask blank of claim 1,
an photoelectron intensity P of 461eV which makes the binding energy in the Ti2P narrow spectrum NU When meeting P NU /P S Greater than 1.05.
3. A mask blank as claimed in claim 1 or 2, wherein,
the ratio of the titanium content in the inner region to the total content of titanium and silicon is 0.05 or more.
4. A mask blank as claimed in claim 1 or 2, wherein,
The total content of titanium, silicon and nitrogen in the internal region is 90 at% or more.
5. A mask blank as claimed in claim 1 or 2, wherein,
the oxygen content of the inner region is 7 at% or less.
6. A mask blank as claimed in claim 1 or 2, wherein,
the surface layer region on the side opposite to the light-transmitting substrate side is a region extending from the surface on the side opposite to the light-transmitting substrate side to a depth of 10 nm.
7. A mask blank as claimed in claim 1 or 2, wherein,
the vicinity area on the light-transmitting substrate side is an area extending from the surface on the light-transmitting substrate side to a depth of 10nm on the opposite side to the light-transmitting substrate.
8. A mask blank as claimed in claim 1 or 2, wherein,
the thin film is a phase-shifting film,
the phase shift film has a transmittance of 1% or more with respect to light having a wavelength of 365nm, and a phase difference of 150 DEG to 210 DEG with respect to light having a wavelength of 365 nm.
9. A mask blank as claimed in claim 1 or 2, wherein,
an etching mask film having a different etching selectivity with respect to the thin film is provided on the thin film.
10. The mask blank of claim 9, wherein,
the etching mask film contains chromium.
11. A transfer mask having a light-transmitting substrate and a film provided on a main surface of the light-transmitting substrate and having a transfer pattern, characterized in that,
the film contains titanium, silicon and nitrogen,
an photoelectron intensity P of 455eV as a binding energy in a narrow spectrum of Ti2P obtained by analyzing an inner region of the film by X-ray photoelectron spectroscopy N The photoelectron intensity of the Si2P narrow spectrum with the binding energy of 102eV is P S When meeting P N /P S A relationship greater than 1.18,
the inner region is a region of the film other than a vicinity region on the light-transmitting substrate side and a surface layer region on the opposite side of the light-transmitting substrate,
the nitrogen content in the internal region is 30 atomic% or more.
12. The transfer mask according to claim 11, wherein,
an photoelectron intensity P of 461eV which makes the binding energy in the Ti2P narrow spectrum NU When meeting P NU /P S Greater than 1.05.
13. A transfer mask according to claim 11 or 12,
the ratio of the titanium content in the inner region to the total content of titanium and silicon is 0.05 or more.
14. A transfer mask according to claim 11 or 12,
the total content of titanium, silicon and nitrogen in the internal region is 90 at% or more.
15. A transfer mask according to claim 11 or 12,
the oxygen content of the inner region is 7 at% or less.
16. A transfer mask according to claim 11 or 12,
the surface layer region on the side opposite to the light-transmitting substrate side is a region extending from the surface on the side opposite to the light-transmitting substrate side to a depth of 10 nm.
17. A transfer mask according to claim 11 or 12,
the vicinity area on the light-transmitting substrate side is an area extending from the surface on the light-transmitting substrate side to a depth of 10nm on the opposite side to the light-transmitting substrate.
18. A transfer mask according to claim 11 or 12,
the thin film is a phase-shifting film,
the phase shift film has a transmittance of 1% or more with respect to light having a wavelength of 365nm, and a phase difference of 150 DEG to 210 DEG with respect to light having a wavelength of 365 nm.
19. A method for manufacturing a transfer mask is characterized by comprising:
A step of preparing the mask blank according to any one of claims 1 to 8;
forming a resist film having a transfer pattern on the thin film;
and performing wet etching using the resist film as a mask, thereby forming a transfer pattern on the thin film.
20. A method for manufacturing a transfer mask is characterized by comprising:
preparing the mask blank according to claim 9 or 10;
forming a resist film having a transfer pattern on the etching mask film;
performing wet etching using the resist film as a mask, and forming a transfer pattern on the etching mask film;
and performing wet etching using the etching mask film having the transfer pattern formed thereon as a mask, thereby forming a transfer pattern on the thin film.
21. A method for manufacturing a display device, comprising:
a step of placing the transfer mask according to any one of claims 11 to 18 on a mask stage of an exposure apparatus;
and a step of irradiating the transfer mask with exposure light and transferring the transfer pattern to a resist film provided on the display device substrate.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2022-009307 | 2022-01-25 | ||
| JP2022009307A JP2023108276A (en) | 2022-01-25 | 2022-01-25 | Mask blank, mask for transfer, method for producing mask for transfer and method for producing display device |
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| Publication Number | Publication Date |
|---|---|
| CN116500852A true CN116500852A (en) | 2023-07-28 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310088032.0A Pending CN116500852A (en) | 2022-01-25 | 2023-01-18 | Mask blank, transfer mask, method for manufacturing transfer mask, and method for manufacturing display device |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP2023108276A (en) |
| KR (1) | KR20230114713A (en) |
| CN (1) | CN116500852A (en) |
| TW (1) | TW202344916A (en) |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2966369B2 (en) | 1996-03-30 | 1999-10-25 | ホーヤ株式会社 | Phase shift mask and phase shift mask blank |
| US6730445B2 (en) | 2002-04-12 | 2004-05-04 | International Business Machines Corporation | Attenuated embedded phase shift photomask blanks |
| JP7059234B2 (en) | 2018-11-30 | 2022-04-25 | Hoya株式会社 | Photomask blank, photomask manufacturing method and display device manufacturing method |
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2022
- 2022-01-25 JP JP2022009307A patent/JP2023108276A/en active Pending
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2023
- 2023-01-05 TW TW112100360A patent/TW202344916A/en unknown
- 2023-01-17 KR KR1020230006740A patent/KR20230114713A/en unknown
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| Publication number | Publication date |
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| TW202344916A (en) | 2023-11-16 |
| JP2023108276A (en) | 2023-08-04 |
| KR20230114713A (en) | 2023-08-01 |
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