CN109298594B - Glass recycling method, recycled glass substrate, and photomask blank and photomask using same - Google Patents
Glass recycling method, recycled glass substrate, and photomask blank and photomask using same Download PDFInfo
- Publication number
- CN109298594B CN109298594B CN201811229615.6A CN201811229615A CN109298594B CN 109298594 B CN109298594 B CN 109298594B CN 201811229615 A CN201811229615 A CN 201811229615A CN 109298594 B CN109298594 B CN 109298594B
- Authority
- CN
- China
- Prior art keywords
- photomask
- glass substrate
- treatment
- thin film
- metal thin
- 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.)
- Active
Links
- 239000000758 substrate Substances 0.000 title claims abstract description 243
- 239000011521 glass Substances 0.000 title claims abstract description 224
- 238000000034 method Methods 0.000 title abstract description 113
- 238000004064 recycling Methods 0.000 title abstract description 14
- 238000007689 inspection Methods 0.000 claims abstract description 34
- 229910052751 metal Inorganic materials 0.000 claims description 81
- 239000002184 metal Substances 0.000 claims description 81
- 239000010409 thin film Substances 0.000 claims description 79
- 238000005530 etching Methods 0.000 claims description 61
- 239000000243 solution Substances 0.000 claims description 54
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 47
- 239000007864 aqueous solution Substances 0.000 claims description 41
- 238000011069 regeneration method Methods 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 230000008929 regeneration Effects 0.000 claims description 26
- 230000001172 regenerating effect Effects 0.000 claims description 14
- 239000003513 alkali Substances 0.000 claims description 6
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 238000000265 homogenisation Methods 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 238000009736 wetting Methods 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 46
- 230000007547 defect Effects 0.000 abstract description 18
- 238000005498 polishing Methods 0.000 abstract description 16
- 230000002950 deficient Effects 0.000 abstract description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 73
- 239000011651 chromium Substances 0.000 description 63
- 229910052804 chromium Inorganic materials 0.000 description 62
- 239000010408 film Substances 0.000 description 60
- 238000010586 diagram Methods 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- 229920005989 resin Polymers 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 238000002474 experimental method Methods 0.000 description 11
- 238000004090 dissolution Methods 0.000 description 10
- 238000007654 immersion Methods 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 239000010453 quartz Substances 0.000 description 9
- 238000003384 imaging method Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000012545 processing Methods 0.000 description 8
- 238000000206 photolithography Methods 0.000 description 7
- 238000004544 sputter deposition Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910000423 chromium oxide Inorganic materials 0.000 description 4
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000010894 electron beam technology Methods 0.000 description 4
- 238000000059 patterning Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000005856 abnormality Effects 0.000 description 3
- 150000001413 amino acids Chemical class 0.000 description 3
- 150000007942 carboxylates Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 238000011179 visual inspection Methods 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- YXTPWUNVHCYOSP-UHFFFAOYSA-N bis($l^{2}-silanylidene)molybdenum Chemical compound [Si]=[Mo]=[Si] YXTPWUNVHCYOSP-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000012790 confirmation Methods 0.000 description 2
- 238000001312 dry etching Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- -1 i.e. Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 229910021344 molybdenum silicide Inorganic materials 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 229920002454 poly(glycidyl methacrylate) polymer Polymers 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 238000001039 wet etching Methods 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 235000004258 Cordia alliodora Nutrition 0.000 description 1
- 244000085692 Cordia alliodora Species 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- SJKRCWUQJZIWQB-UHFFFAOYSA-N azane;chromium Chemical compound N.[Cr] SJKRCWUQJZIWQB-UHFFFAOYSA-N 0.000 description 1
- HKVFISRIUUGTIB-UHFFFAOYSA-O azanium;cerium;nitrate Chemical compound [NH4+].[Ce].[O-][N+]([O-])=O HKVFISRIUUGTIB-UHFFFAOYSA-O 0.000 description 1
- CXOWYMLTGOFURZ-UHFFFAOYSA-N azanylidynechromium Chemical compound [Cr]#N CXOWYMLTGOFURZ-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 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 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
- G03F1/60—Substrates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B5/00—Operations not covered by a single other subclass or by a single other group in this subclass
-
- 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
- C03C15/00—Surface treatment of glass, not in the form of fibres or filaments, by etching
-
- 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
- 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
-
- 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
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
- G03F1/68—Preparation processes not covered by groups G03F1/20 - G03F1/50
- G03F1/72—Repair or correction of mask defects
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Surface Treatment Of Glass (AREA)
- Preparing Plates And Mask In Photomechanical Process (AREA)
Abstract
The present invention relates to a method for recycling a photomask used up in the production of various flat plates or a photomask which is defective in a photomask production process as a novel photomask glass substrate, a photomask glass substrate recycled by the recycling method, and a photomask blank and a photomask using the photomask glass substrate. A recycled glass substrate with few defects can be obtained at low cost by performing a treatment for uniformizing wettability until no original pattern trace appears in a breath image inspection without performing a conventional physical polishing treatment on the surface of the recycled glass substrate.
Description
The present application is a divisional application of an invention patent application having an international application date of 2013, 9/19, and an application number of 201380047359.8, entitled "glass recycling method, recycled glass substrate, and photomask blank and photomask using the same".
Technical Field
The present invention relates to a method for recycling a photomask, which is patterned with a metal thin film and used for production in a photolithography process (hereinafter also referred to as photolithography) of various flat panels, or a photomask, which is defective in a photomask production process, as a novel photomask glass substrate, a photomask glass substrate recycled by the recycling method, and a photomask blank and a photomask using the photomask glass substrate.
Background
A photomask generally used for manufacturing a flat plate or the like is manufactured by: a photomask blank having a light-shielding layer formed thereon is prepared by laminating a metal thin film of chromium, chromium oxide, chromium nitride or the like on a low-expansion glass substrate such as synthetic quartz, and a pattern is formed on the photomask blank by EB (Electron Beam) drawing or laser drawing using a photolithography method.
Such a photomask is used in various exposure apparatuses for forming pixels and the like, such as liquid crystal display apparatuses, organic EL display apparatuses, and high-precision touch panels. Since synthetic quartz is used for a photomask used for these products in accordance with quality performance, the size of the photomask has been increased with the recent increase in the size of the panel, and the photomask glass substrate has become more expensive, it has become an important technique to reuse a used photomask or a defective photomask.
In the photomask substrate, synthetic quartz is generally used as a material of the glass substrate for a photomask from the viewpoint of quality and height, and since the glass substrate has a size of 320mm × 300mm in the 1 st generation substrate of the flat substrate of a liquid crystal display device and a size of 330mm × 450mm slightly larger than the glass substrate for a flat substrate, the collective exposure is performed.
In such a flat plate, the 5 th generation of the flat plate substrate is 1000mm × 1200mm, and the photomask substrate size is usually 520mm × 800mm or 800mm × 920 mm. The flat substrate of the 8 th generation is 2160mm × 2460mm, and the photomask substrate used therein has dimensions 1220mm × 1400mm and the like.
On the other hand, a high-quality glass substrate for a photomask made of synthetic quartz is required to reduce the cost of a panel since the cost is reduced, and therefore, a regeneration process of a used photomask or a defective photomask is performed.
Typically, the photomask pattern of each article of each component of the plate is not the same, and at the end of the article production, the photomask is no longer needed.
In addition, in the photomask process, defective products generated in the manufacturing process and defective products generated in the inspection process may also be generated.
In order to reuse the used photomask substrate or the defective photomask substrate, the metal thin film having a pattern formed thereon is dissolved and removed by an etching solution to be in a state of a glass blank.
However, the used photomask substrate or the substrate on which the metal thin film pattern has been formed in the photomask process has the following problems: when only the metal thin film pattern is dissolved and removed by the etching solution and washed, if the metal thin film is formed again and the substrate is patterned by photolithography, the original pattern trace is present and the pattern defect is easily generated.
Therefore, when the photomask is reused, the metal thin film having a pattern formed thereon is dissolved and removed by the etching solution to be a glass blank, and then the glass surface is physically polished with an abrasive to clean and uniformize the glass surface, and then washed to remove the abrasive used for polishing, thereby reusing the glass substrate as a photomask glass substrate.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2011-148026
Patent document 2: japanese laid-open patent publication No. 2-102142
Disclosure of Invention
Problems to be solved by the invention
A method for recycling a conventional photomask glass substrate will be described with reference to fig. 2.
First, the metal thin film with a pattern formed thereon is dissolved and removed by an etching solution to be in a glass blank state (K1), and then physically polished by an abrasive such as cerium oxide to make the glass surface uniform. Polishing was performed using a polishing apparatus for rough polishing and a polishing apparatus for final surface polishing as polishing apparatuses (K2). Subsequently, the substrate was washed using an abrasive removing and washing apparatus for removing the abrasive and a final washing apparatus (K3), and the appearance was inspected again (K4), thereby producing a regenerated substrate.
Further, a waste treatment apparatus for removing the polishing agent during cleaning is required as an auxiliary apparatus, and the apparatus is expensive, and the installation space of the apparatus needs to be enlarged, and there are cases where the treatment time is long, the photomask surface is damaged by the contamination of foreign matter during polishing, and the flatness of the photomask surface is impaired, which causes problems in production cost and production efficiency.
In the present invention, a regenerated substrate with few pattern defects can be obtained at low cost by performing wet wettability equalization treatment without physically polishing the glass substrate from which the metal thin film has been dissolved and removed.
Means for solving the problems
The 1 st aspect of the present invention for solving the above problems is:
a method for regenerating a glass substrate for a photomask, which comprises patterning at least one surface of the glass substrate with a metal thin film,
after the metal thin film formed on the glass substrate is dissolved and removed by an etchant, wet wettability leveling processing is performed until the pattern does not appear in a breath image inspection.
The invention according to claim 2 for solving the above problems is:
the method for recycling a glass substrate for a photomask according to claim 1, wherein the wet wettability equalizing treatment and the breath image inspection are repeated.
The 3 rd aspect of the present invention for solving the above problems is:
the method for recycling a photomask glass substrate according to claim 1 or 2, wherein the wet wettability equalizing treatment is a treatment for equalizing the wettability of the surface of the photomask glass substrate.
The 4 th aspect of the present invention for solving the above problems is:
the method for regenerating a glass substrate for a photomask according to any one of claims 1 to 3, wherein the wet wettability equalizing treatment is a treatment with an alkaline aqueous solution.
The 5 th aspect of the present invention for solving the above problems is:
the method for recycling a glass substrate for a photomask according to claim 4, wherein the alkali component of the alkaline aqueous solution is potassium hydroxide.
The present invention for solving the above problems obtains the 6 th aspect as follows:
a glass substrate for a photomask, which is a glass substrate obtained by regenerating a photomask having a metal thin film pattern formed on at least one surface of a glass substrate,
on the glass substrate, a metal thin film formed as a photomask is dissolved and removed by an etching solution,
the glass substrate was subjected to wet-type wettability uniformization treatment until the pattern was not formed in the exhale image inspection.
The 7 th aspect of the present invention for solving the above problems is:
the photomask glass substrate according to claim 6, wherein the wet wettability equalizing treatment and the breath image inspection are repeated.
The 8 th aspect of the present invention for solving the above problems is:
the photomask glass substrate according to claim 6 or 7, wherein the wettability of the surface of the photomask glass substrate is uniformized by the wet wettability uniformizing treatment.
The 9 th aspect of the present invention for solving the above problems is:
the photomask glass substrate according to any one of claims 6 to 8, wherein the wet wettability equalizing treatment is a treatment with an alkaline aqueous solution.
A 10 th aspect of the present invention for solving the above problems is:
the glass substrate for a photomask according to claim 9, wherein the alkali component of the alkaline aqueous solution is potassium hydroxide.
An 11 th aspect of the present invention for solving the above problems is:
the glass substrate for a photomask according to any one of claims 6 to 10, wherein the difference in contact angle of water is 1 degree or less on the surface of the glass substrate for a photomask subjected to the regenerating treatment.
The 12 th aspect of the present invention for solving the above problems is:
a photomask blank using the photomask glass substrate according to any one of claims 6 to 11.
The 13 th aspect of the present invention for solving the above problems is:
a photomask using the photomask blank according to claim 12.
The 14 th aspect of the present invention for solving the above problems is:
a method for manufacturing a regenerated glass substrate for a photomask, comprising:
a dissolving and removing step of dissolving and removing a metal thin film formed in a pattern on one surface of a glass substrate from a photomask having the glass substrate and the metal thin film by using an etching solution; and
and a wet wettability equalizing step of bringing an alkaline aqueous solution into contact with the surface of the glass substrate after the dissolution removal step to perform wet wettability equalizing treatment.
The 15 th aspect of the present invention for solving the above problems is:
the method for producing a regenerated glass substrate for a photomask according to claim 14, wherein the alkali component of the alkaline aqueous solution is potassium hydroxide.
The 16 th aspect of the present invention for solving the above problems is:
a method for manufacturing a photomask, comprising:
a regeneration treatment step of forming a regenerated glass substrate for a photomask by a regeneration treatment method in which a metal thin film of a glass substrate for a photomask having a pattern formed on at least one surface thereof by forming the metal thin film is dissolved and removed by an etching solution and then subjected to a wet wettability equalization treatment until the pattern does not appear in a breath image inspection;
a mask blank forming step of forming a mask blank by forming a metal thin film on at least one surface of the regenerated glass substrate for a photomask;
a resist forming step of forming a resist in a pattern on the metal thin film; and
and an etching step of etching the exposed portion of the metal thin film on which the resist is formed.
The 17 th aspect of the present invention for solving the above problems is:
a method for manufacturing a photomask, comprising:
a regeneration treatment step of forming a regenerated glass substrate for a photomask by performing a dissolution removal step of dissolving and removing a metal thin film formed in a pattern on one surface of a glass substrate from a photomask including the glass substrate and the metal thin film by using an etching solution and a wet wettability equalization treatment step of bringing an alkaline aqueous solution into contact with the surface of the glass substrate after the dissolution removal step to perform a wet wettability equalization treatment;
a mask blank forming step of forming a mask blank by forming a metal thin film on at least one surface of the regenerated glass substrate for a photomask;
a resist forming step of forming a resist in a pattern on the metal thin film; and
and an etching step of etching the exposed portion of the metal thin film on which the resist is formed.
The wet wettability equalizing treatment described in the claims and the specification of the present invention is preferably performed by a treatment step of immersing the surface of the glass substrate in an aqueous chemical solution, rather than a surface treatment step such as a physical polishing step or dry etching.
The breath image examination described in the claims and the specification of the present invention is: an inspection method in which water vapor is attached to the surface of a glass substrate and the wettability of the surface is inspected visually or automatically.
The breath examination will be described in detail in describing an embodiment of the present invention.
The metal thin film described in the claims and the specification of the present invention is a substance that functions as a light-shielding film, a translucent film, or the like in a photomask, and the concept of a metal material includes not only a simple metal but also a metal alloy, a nitride, an oxide, an oxynitride of a metal element, or a compound containing another metal element.
Effects of the invention
In the regeneration treatment of the used photomask or the photomask with poor process, the physical grinding process is not needed, the regeneration treatment of the glass substrate for the photomask is easy, the regeneration cost can be reduced, and the manufacturing cost can be reduced in the blank for the photomask and the photomask.
Drawings
FIG. 1 is a process diagram for regenerating a photomask glass substrate including wet wettability equalization treatment.
FIG. 2 is a process diagram of a regeneration treatment of a photomask glass substrate including a polishing step.
Fig. 3 is a process diagram of the photomask substrate.
Fig. 4 is a graph showing the amount of glass etched in preliminary experiment 1.
Fig. 5 is a schematic diagram illustrating a reproduction process and an exhalation image of a pattern. a is a diagram showing an appearance of the photomask. b is a diagram showing a breath image of the substrate with the pattern etched. And c is an appearance diagram after the wettability equalizing treatment.
Fig. 6 is a schematic diagram illustrating preparatory experiment 3. a is a view showing a state in which a half surface of a substrate on which a pattern has been etched is immersed in a wettability equalizing treatment liquid. b is a diagram showing an exhalation image of the substrate of a. And c is an appearance view showing the surface of the chromium blank on which the chromium film was formed on the substrate of a. d is a diagram illustrating inspection defects of the substrate on which the pattern is formed on the substrate c.
Fig. 7 is an explanatory diagram for explaining an example of an expiratory image examination used in the present invention.
Fig. 8 is an explanatory view for explaining another example of an expiratory image examination used in the present invention.
Detailed Description
The method for recycling a photomask glass substrate, the method for producing a photomask, and the like according to the present invention will be described below.
A. Regeneration method of glass substrate for photomask
Before describing the present embodiment of the present invention, a process for manufacturing a photomask used in a process for manufacturing a flat panel display panel will be described with reference to (P1) to (P5) of fig. 3.
(P1) A photomask blank having a 2-layer structure of a chromium film 2 was prepared by sputtering pure chromium with an increased optical density on a synthetic quartz substrate and then forming a chromium oxide film for suppressing surface reflection.
(P2) applying a photosensitive resin to the photomask blank and baking the photosensitive resin, (P3) performing EB drawing or laser drawing in accordance with the pattern data, developing the photosensitive resin, patterning the photosensitive resin, (P4) etching the chromium film and the chromium oxide film, and (P5) removing the resist by a stripping solution after dissolving the part not covered with the resist to prepare a photomask.
The photomask is subjected to inspection and correction processes after being washed, and a thin film (pellicle) is attached to the surface of the photomask as necessary.
The photomask manufactured by the above process is used in various exposure devices in the production of panels for various flat panel displays.
Next, a method for regenerating a photomask blank according to the present embodiment of the invention will be described with reference to (S1) to (S4) of fig. 1.
(S1) first, the photomask blank patterned with the chromium film is immersed in a chromium etching solution, which is an aqueous solution of ammonium cerium nitrate, perchloric acid, nitric acid, or the like, to dissolve the chromium film, and then washed with pure water to remove the pattern of the chromium film.
(S2) Next, the glass is immersed in a wettability equalizing treatment liquid for equalizing the wettability of the glass surface after the chromium film is removed by etching.
(S3) the substrate is washed and dried.
The wet-type wettability equalizing treatment liquid is an aqueous solution containing an alkali as a main component, and is effectively constituted by a continuous apparatus which is a series of the following washing and drying steps.
The device can also be composed of: a vertical conveyance system in which a regenerated glass substrate is vertically placed in a holding container, a tank for circulating a wettability-equalizing treatment liquid, a tank for rinsing with pure water, and the like are sequentially disposed, and the glass substrate is immersed and dried; or a horizontal conveyance system in which each sheet is horizontally conveyed, a wettability-equalizing treatment liquid is applied from above through a nozzle, then rinsing is performed with pure water, and finally drying is performed with air.
(S4) the prepared regenerated substrate was inspected similarly to the inspection of the photomask glass, but the inspection by the expiration method was added as the inspection for confirming the regeneration state, and it was confirmed that no pattern trace was present.
If the pattern trace formed by the chrome film appears in the breath image inspection (S4), the wet wettability equalizing treatment (S2) and the washing and drying treatment (S3) are repeated until the pattern trace does not appear in the breath image inspection.
Here, the expiratory imaging method described in the claims and the specification of the present invention will be described.
The exhalation imaging method is: a method of inspecting a photomask glass substrate for a photomask, wherein water vapor of pure water is condensed on the surface of the photomask glass substrate, and a difference in the surface state of the glass surface is detected from a difference in the state of condensation.
When the surface state of the glass substrate varies, the size of water droplets generated by condensation of water vapor varies, and the state of light scattering varies as a whole, so that a slight difference in the partial surface state can be visually detected.
The term "visual confirmation of an expired air image" means: in a state where water vapor was condensed on the glass surface, the appearance of the original pattern trace formed by the chromium film was observed. Fig. 5a shows a photomask having a pattern formed of a chromium film, in which a frame-shaped chromium film portion (2a) is present on the outer periphery of a photomask substrate, and image portions (3a) in which the chromium film is finely patterned are arranged on a plurality of surfaces in the photomask substrate. FIG. 5b is a photograph showing the glass substrate after the chromium film was removed by etching by the expiration photograph method. Thus, the outline of the patterns (2b and 3b) can be visually confirmed.
The phrase "no exhalation was visually confirmed" means that: in a state where water vapor was condensed on the glass surface, the appearance of the original pattern mark formed by the chromium film was not observed. As shown in FIG. 5c, the patterns (2b and 3b) formed by the original chromium film were not observed.
Specific conditions of the exhaled breath image inspection method and the like will be described in the section "b" method for manufacturing a regenerated glass substrate for a photomask "described later.
Next, the problems of the photomask blank and the photomask using the glass substrate, which has been regenerated by dissolving and removing the patterned chrome film only with the etching solution without the wettability equalizing treatment, will be described in detail.
The photomask blank was confirmed to have an original pattern trace by the reflective visual inspection, and when the photomask blank was used to perform patterning again, a white defect as shown in fig. 6e was likely to occur at the edge of the image portion of the pattern.
Next, the wet wettability equalizing treatment, which is an alternative to the conventional physical polishing method, will be described in further detail by explaining the experimental results of the preliminary experiments 1 to 3.
The regenerated glass substrate from which the chromium film was removed was immersed in a hydrofluoric acid aqueous solution as solution 1, a potassium hydroxide aqueous solution as solution 2, and an aqueous solution in which an organic phosphate, a carboxylate, an amino acid, and a surfactant were added to potassium hydroxide as solution 3, and immersion evaluation was performed.
As for the evaluation content, the inspection of pattern traces by the exhalation imaging method and the glass etching amount of the surface of the regenerated glass substrate which was immersed for a predetermined time and then washed and dried were evaluated.
The treatment was carried out under the conditions of immersion liquid temperature of 25 ℃ and immersion time of 2 hours, 5 hours and 10 hours.
The results of the preliminary experiment 1 after 10-hour immersion are shown in table 1 and described below.
[ Table 1]
In both of the 5% aqueous solution and the 10% aqueous solution of hydrofluoric acid (solution 1), the amount of glass etched was large, and a pattern trace was observed by an expiratory imaging method.
The etching amount of the glass substrate immersed for 10 hours was about 15 μm at a concentration of 5% and about 40 μm at a concentration of 10%.
In the aqueous solution (solution 2) of 5% to 30% potassium hydroxide, no pattern mark was observed by the expiration photograph method, and the amount of glass etched was smaller than that of hydrofluoric acid treatment, but the amount of etching increased as the concentration of potassium hydroxide increased.
The etching amount of the glass substrate immersed for 10 hours was about 1 μm at a concentration of 5%, about 3 μm at a concentration of 10%, about 4 μm at a concentration of 15%, and about 12 μm at a concentration of 30%.
In an aqueous solution (solution 3) obtained by adding an organic phosphate, a carboxylate, an amino acid and a surfactant to potassium hydroxide, no pattern mark was observed by the expiration image method, and the glass etching amount after 10 hours of immersion was 1 μm or less.
When the etching amount of the glass is large, damage such as a sink defect is considered to occur in the glass, and therefore, a smaller etching amount is preferable.
[ preliminary experiment 2]
On the main surfaces of 3 kinds of regenerated glass substrates, i.e., substrates in which the chromium film was dissolved and removed by an etching solution and the original pattern traces were confirmed by the expiration method and substrates in which the pattern traces were not confirmed by the expiration method by immersion treatment in the above solutions 2 and 3, respectively, chromium was again formed by sputtering, and the surfaces were irradiated with light to detect the presence or absence of the pattern traces by visual inspection with reflection.
Results of preliminary experiment 2
Although the original pattern traces were not observed even after the chromium film formation for the regenerated glass substrates in which the immersion treatment was performed in each of the solutions 2 and 3 and the original patterns were not observed by the expiratory imaging method, the pattern traces were also observed after the chromium film formation for the substrates in which the immersion treatment was not performed in the solutions 2 and 3 and the original patterns were observed by the expiratory imaging method.
Next, for a substrate on which the chromium film was dissolved and removed by the etching solution and the trace of the original pattern was not observed by the expiration method, the substrate was immersed in the solution 2 and the solution 3 on one side half surface (W) as shown in fig. 6a, and the effect in the same substrate was observed.
Results of preliminary experiment 3
As shown in fig. 6b, after the one-side half surface immersed in the solution 2 or the solution 3 was washed with water and dried, the original pattern trace was not observed by the exhaling method, and as shown in fig. 6c, the pattern trace was not observed on the one-side half surface immersed after the chromium film formation. However, the one-side half surface which was not treated with the solution 2 or the solution 3 showed a pattern mark after chromium deposition.
Table 2 shows the results of measuring the contact angle after removing the chromium film by etching and after performing immersion treatment in the solutions 2 and 3.
For the measurement of the contact angle, after removing the chromium film by etching and after immersing the same portion in each of the solutions 2 and 3, the contact angle was measured with respect to the glass surface of the portion where the chromium film was formed and the portion where the chromium film was not formed.
Table 2 shows the results of the contact angle measurement.
The contact angle was measured by means of a flat contact angle meter FPD-MH20, manufactured by Coulter's interface science.
After the chromium film is etched and removed, the contact angle of the original chromium part is 19.2-19.9 degrees; in contrast, the original glass portion is 16.3 to 16.5 degrees.
The difference in contact angle between the original chromium portion and the original glass portion was about 3 degrees, and it is considered that the original pattern trace could be confirmed by the expiratory imaging method based on the difference.
Next, as for the contact angles after immersion in the solutions 2 and 3, the contact angles of the original chromium portion and the original glass portion were 17.2 degrees to 17.8 degrees as shown in table 2, and the difference between the contact angles was 1 degree or less.
More specifically, in the substrate immersed in the aqueous potassium hydroxide solution of each concentration in the solution 2, the difference between the contact angle of the original chromium portion and the contact angle of the original glass portion is 1 degree or less. In addition, even in the substrate immersed in the solution 3, the difference between the contact angle of the original chromium portion and the contact angle of the original glass portion is 1 degree or less.
This suggests that the original pattern cannot be confirmed by the exhalation imaging method.
[ Table 2]
Next, a photosensitive material was applied to the chromium film-formed substrate, and a pattern was formed again by photolithography.
Fig. 6d shows the inspection result of the photomask after the patterning. The appearance inspection apparatus 51MD manufactured by Lasertec was used as the inspection apparatus. Confirming that a large amount of white defects are generated at the edge part of an image part of the pattern in the half face of the original pattern by an exhalation image method; on the other hand, it was not confirmed by the exhalation method that almost no white defects were generated in the half-plane of the original pattern.
When the position of the white defect is analyzed in detail, the white defect intersects the original pattern trace, and the shape of the white defect is also schematically shown in fig. 6 e.
Through the above preliminary experiments, it was confirmed that: the glass substrate, in which the original pattern trace was confirmed by the aerial image method, was not physically polished but subjected to only wet processing, so that the original pattern trace could be eliminated in a state that could not be confirmed by the aerial image method. And it was confirmed that: by making the original pattern trace disappear in the exhalation image method, the pattern defect can be improved.
In the above description, the method of regenerating a photomask having a metal thin film made of a chromium-based material was described as an example, but the same regeneration method can be applied to a photomask having a metal thin film made of another metal material. The details of the metal thin film will be described in "b" method for manufacturing a regenerated glass substrate for a photomask "described later.
B. Method for manufacturing regenerated glass substrate for photomask
The method for manufacturing a regenerated glass substrate for a photomask (hereinafter, may be simply referred to as a regenerated glass substrate) of the present invention includes: a dissolving and removing step of dissolving and removing a metal thin film formed in a pattern on one surface of a glass substrate from a photomask having the glass substrate and the metal thin film by using an etching solution; and a wet wettability equalizing step of bringing an alkaline aqueous solution into contact with the surface of the glass substrate after the dissolution removal step to perform wet wettability equalizing treatment.
According to the present invention, since the wet wettability equalizing treatment step is provided, the wettability of the surface of the regenerated glass substrate can be equalized, and therefore, when a photomask is manufactured using the regenerated glass substrate, the metal thin film can be favorably formed in a pattern on the surface of the regenerated glass substrate, and peeling or the like of the metal thin film can be prevented.
Here, as described above, when a photomask is manufactured again using the glass substrate after the dissolution and removal step (hereinafter, this may be referred to as an untreated glass substrate), there are the following problems: the metal thin film formed on the untreated glass substrate is likely to be peeled off and to have pattern defects. In contrast, in the conventional methods for producing recycled glass substrates, a method of polishing the surface of an untreated glass substrate to make the surface state uniform is used, but there is a problem of production cost consumption.
The present inventors have conducted intensive studies as a method for surface treatment of an untreated glass substrate instead of polishing, and as a result, have found that: when an untreated glass substrate is used as a photomask, there is a difference in wettability between a portion where the glass substrate is exposed and a portion where a metal thin film is formed, the difference in wettability causes peeling of the metal thin film, and the wettability of the surface of the untreated glass substrate can be made uniform by performing a wet wettability uniformizing treatment in which an alkaline aqueous solution is brought into contact with the untreated glass substrate.
The invention has the important characteristics that the points are found.
The method for producing a regenerated glass substrate for a photomask according to the present invention will be described in detail below.
1. Dissolution removal step
The dissolving and removing step of the present invention is a step of dissolving and removing a metal thin film formed in a pattern on one surface of a glass substrate from a photomask including the glass substrate and the metal thin film by using an etching solution. This step is a step of obtaining an untreated glass substrate.
First, a photomask used in this step will be described.
The photomask includes a glass substrate and a metal thin film formed in a pattern on the glass substrate. The photomask is used after a product is manufactured by a photolithography process, or is a photomask itself that is defective during manufacturing.
The glass substrate may be the same as a glass substrate used for a general photomask, and examples thereof include synthetic quartz glass and Pyrex (registered trademark) glass. The thickness of the glass substrate is not particularly limited, and may be appropriately selected depending on the use of the photomask.
The metal thin film used for the photomask may be the same as that used for a general photomask, and examples thereof include: a thin film containing, as a main component, any one metal element selected from chromium (Cr), tantalum (Ta), molybdenum (Mo), titanium (Ti), zirconium (Zr), and the like; a thin film mainly composed of any one of a nitride, an oxide, and an oxynitride of the metal element; or a molybdenum silicide (MoSi) thin film, etc. In the present invention, it is particularly preferable that the metal thin film is made of a chromium-based material such as chromium, chromium nitride, chromium oxide, or chromium oxynitride.
The thickness of the metal thin film may be appropriately selected according to the use of the photomask, and is, for example, about 30nm to 150 nm.
The metal thin film in the photomask is generally formed in a predetermined pattern shape on the surface of the glass substrate. The pattern of the metal thin film may be appropriately selected according to the use of the photomask.
The etching solution used in this step can be appropriately selected according to the type of the metal thin film. As such an etching solution, a general etching solution can be used, and for example, when a metal thin film is formed of a chromium-based material, the etching solution described in the above "method for regenerating a photomask glass substrate" can be used. Further, as an etching method, for example, a method of immersing the surface of the photomask on the side of the metal thin film in an etching solution can be cited.
In this step, after the metal thin film is dissolved and removed from the photomask, a cleaning treatment is usually performed.
2. Wet-type wetting homogenization treatment process
The wet wettability equalizing treatment step in the present invention is a step of bringing an alkaline aqueous solution into contact with the surface of the glass substrate after the dissolution removal step to perform wet wettability equalizing treatment.
In the following description, a glass substrate subjected to wet-type wettability equalizing treatment may be referred to as a "treated glass substrate", and a glass substrate having the wettability of the surface of the glass substrate equalized may be referred to as a "regenerated glass substrate".
As the alkaline aqueous solution used in this step, for example, an alkaline aqueous solution containing potassium hydroxide (KOH) as an alkaline component can be suitably used. When the alkaline aqueous solution contains potassium hydroxide, the concentration (content) of potassium hydroxide in the alkaline aqueous solution is not particularly limited as long as the wettability of the surface of the regenerated glass substrate can be made uniform, and is preferably within a range of 5% to 30%, and particularly preferably within a range of 5% to 15%. When the concentration of potassium hydroxide is within the above range, the wettability of the surface of the glass substrate can be suitably made uniform.
To the aqueous alkaline solution used in this step, for example, an organic phosphate, a carboxylate, an amino acid, a surfactant, and the like may be added.
As a method of bringing the alkaline aqueous solution into contact with the surface of the untreated glass substrate, for example, a method of immersing the untreated glass substrate in the alkaline aqueous solution, a method of blowing the alkaline aqueous solution to the metal thin film removal side surface of the untreated glass substrate using a nozzle, a sprayer, or the like can be used.
The inventors confirmed that the wettability of the surface of the treated glass substrate was uniform, that is, a regenerated glass substrate was formed, by performing an expiratory image check.
The method for examining an expiratory image used in the present invention will be described in detail below.
Fig. 7(a) and (b) are explanatory views for explaining an example of the method for examining an expiratory image used in the present invention. In the breath image inspection method of the present invention, first, as shown in fig. 7(a), a container 10 capable of horizontally placing a processed glass substrate 1 'is prepared in an environment of normal temperature and humidity (23 ℃, humidity 50%), and the processed glass substrate 1' is horizontally placed such that a surface subjected to wet wettability equalizing processing (hereinafter, sometimes referred to as a processing surface X) faces the bottom surface of the container 10. At this time, the processing surface X of the processed glass substrate 1' is disposed at a height of about 15cm from the bottom surface of the container 10.
Subsequently, as shown in FIG. 7(b), pure water 20 of about 80 ℃ is poured to a height of about 1 to 2cm from the bottom of the container 10, and left to stand for 1 minute to attach water vapor 21 to the processing surface X of the processed glass substrate 1'. Under a fluorescent lamp, the water vapor 21 adhering to the processing surface X of the processed glass substrate 1 'is observed from the upper side of the container 10 in a see-through manner from the surface Y of the processed glass substrate 1' opposite to the processing surface X.
When the expired image is not visually confirmed, it can be judged that the wettability of the surface of the treated glass substrate is uniform, and when the expired image is visually confirmed, it can be judged that the wettability of the surface of the treated glass substrate is not uniform.
The determination that the expired air image is not visually recognized and that the expired air image is visually recognized are explained in the above-mentioned "a. method for regenerating a photomask glass substrate", and therefore, the explanation thereof is omitted here.
In this step, the above-described breath image inspection may be performed on the untreated glass substrate before the wet wettability equalizing treatment.
When the wettability of the glass substrate is not uniform after the treatment, the wet wettability equalizing treatment and the breath image inspection are usually performed alternately until the wettability of the surface of the glass substrate is equalized after the treatment.
When the method for producing a regenerated glass substrate for a photomask according to the present invention is carried out in a production line, the present step can be carried out, for example, as follows.
First, an alkaline aqueous solution was brought into contact with the surface of an untreated glass substrate under various conditions, and optimum conditions for wet-type wettability uniformization treatment were set. In order to examine the optimum conditions, the wettability of the surface of the glass substrate is generally determined by the above-described expiration image inspection method.
Next, in the production line, wet-type wettability equalizing treatment is performed on a plurality of untreated glass substrates under the above-described optimum conditions. In this case, although whether or not the wettability of the glass substrate is uniform after the in-line treatment can be confirmed by the above-described breath image inspection method, the following breath image inspection method (line breath image inspection method) can be used as a simpler confirmation method.
Fig. 8 is an explanatory diagram for explaining another example of the expiratory image examination method used in the present invention.
The treated glass substrate 1 'is fixed by a fixing device 50 or the like in an atmosphere of normal temperature and humidity (23 ℃ C., humidity 50%), and the water vapor 21 of pure water of 80 ℃ is attached to the treated surface X of the treated glass substrate 1' by a steamer 30 or the like. After the water vapor 21 is adhered, the processed surface X of the processed glass substrate 1' is irradiated with light 41 by a projector 40 and observed.
As the light projector, a general light projector can be used. The steam generator is not particularly limited in its form as long as it can attach water vapor to the treated surface of the treated glass, and a general steam generator can be used. Examples of the steam generator include a hand-held steam generator SSH-601 manufactured by Kawasaki electric machinery, Inc.
In this step, the regenerated glass substrate is usually subjected to a washing and drying treatment after the wet wettability equalizing treatment.
In addition, the apparatus configuration (apparatus) described in the above "method for recycling a photomask glass substrate" can be suitably used in this step.
3. Others
The method for producing a regenerated glass substrate for a photomask of the present invention is not particularly limited as long as it has the dissolution removal step and the wet wettability equalizing treatment step, and other steps may be performed as necessary.
The regenerated glass substrate for a photomask of the present invention can be used as a glass substrate for a photomask.
C. Method for manufacturing photomask
The photomask manufacturing method of the present invention has 2 modes. These two modes will be described below.
1. Mode 1
The method for manufacturing a photomask according to the present invention is the method for manufacturing a photomask according to the first aspect, comprising: a regeneration treatment step of forming a regenerated glass substrate for a photomask by a regeneration treatment method in which a metal thin film of a glass substrate for a photomask having a pattern formed on at least one surface thereof by forming the metal thin film is dissolved and removed by an etching solution and then subjected to a wet wettability equalization treatment until the pattern does not appear in a breath image inspection; a mask blank forming step of forming a mask blank by forming a metal thin film on at least one surface of the regenerated glass substrate for a photomask; a resist forming step of forming a resist in a pattern on the metal thin film; and an etching step of etching the exposed portion of the metal thin film on which the resist is formed.
According to this aspect, by having the above-described regeneration treatment step, even when a regenerated glass substrate is used, a photomask having a metal thin film with a good pattern shape can be produced while preventing peeling of the metal thin film.
(1) Regeneration treatment step
The regeneration treatment step used in the present embodiment is a step of forming a regenerated glass substrate for a photomask by a regeneration treatment method in which a metal thin film of a photomask glass substrate having at least one surface on which a pattern is formed is dissolved and removed by an etching solution and then subjected to a wet wettability equalizing treatment until the pattern does not appear in a breath image inspection.
The recycling method used in the present embodiment is the same as that described in the above "a.
(2) Mask blank forming process
In the mask blank forming step used in the present embodiment, a metal thin film is formed on at least one surface of the regenerated glass substrate for a photomask to form a mask blank.
The materials used for the metal thin film, the thickness of the metal thin film, and the like are the same as those described in the above "method for manufacturing a recycled glass substrate for a photomask", and therefore, the description thereof will be omitted here.
As a method for forming a metal thin film, for example, a vapor deposition method and a sputtering method can be cited as a method for forming a metal thin film used for a general photomask.
(3) Resist Forming Process
The resist forming step used in the present embodiment is a step of forming a resist in a pattern on the metal thin film.
In this step, a resist film is usually formed on a thin metal film, and the resist film is exposed to light and then developed to form a resist having a predetermined pattern shape.
The resist film is formed using a photosensitive resin. The photosensitive resin used for the resist film may be a positive photosensitive resin or a negative photosensitive resin, similar to a general photosensitive resin. Examples of the positive photosensitive resin include phenol epoxy resins (phenol epoxy resins), acrylic resins, polyimides, and cyclic olefins. Specific examples thereof include IP3500 (manufactured by TOK corporation), PFI27 (manufactured by sumitomo chemical corporation), ZEP7000 (manufactured by ZEON corporation), and the like. On the other hand, examples of the negative photosensitive resin include acrylic resins. Specific examples thereof include polyglycidyl methacrylate (PGMA) and chemically amplified SAL601 (Cypres).
The thickness of the resist film is not particularly limited, and is, for example, in the range of 10nm to 10 μm.
As the method of forming the resist film, a known method can be used.
The exposure method used in this step is not particularly limited as long as a desired pattern shape can be drawn on the resist film. For example, a laser drawing method, an EB drawing method, or the like can be used. The exposure conditions and the like may be the same as those used in the production of a general photomask, and therefore, the description thereof will be omitted here.
As a method of developing the resist film, for example, a method using a developer solution and the like can be cited. The type of the developer can be a general developer, and is preferably selected appropriately according to the type of the photosensitive resin. Specific examples of the developing solution include: alkali developing solutions such as tetramethylammonium aqueous solution, potassium hydroxide aqueous solution, sodium hydroxide aqueous solution, and sodium carbonate aqueous solution; and acid developers such as hydrochloric acid aqueous solution, acetic acid aqueous solution, sulfuric acid aqueous solution, and phosphoric acid aqueous solution.
(4) Etching process
The etching step used in the present embodiment is a step of etching the exposed portion of the metal thin film on which the etchant is formed.
As the etching method of the metal thin film, a wet etching method or a dry etching method can be applied. In this step, a wet etching method is particularly preferably used. This is because it is more advantageous in terms of cost.
When the metal thin film is a film made of a chromium-based material, a wet etchant obtained by adding perchloric acid to cerium ammonium nitrate can be suitably used.
After the etching, the resist is usually stripped off, and the photomask is usually cleaned.
(5) Others
The method for manufacturing a photomask of the present embodiment is not particularly limited as long as it has the above-described regeneration treatment step, resist formation step, and etching step, and any additional steps may be appropriately selected.
The photomask manufactured by the method for manufacturing a photomask according to the present embodiment can be used in a photolithography process for manufacturing various flat panels, circuit boards, and the like.
2. Mode 2
The invention provides a method for manufacturing a photomask, according to claim 2, comprising: a regeneration treatment step of forming a regenerated glass substrate for a photomask by performing a dissolution removal step of dissolving and removing a metal thin film formed in a pattern on one surface of a glass substrate from a photomask including the glass substrate and the metal thin film by using an etching solution and a wet wettability uniformization treatment step of bringing an alkaline aqueous solution into contact with the surface of the glass substrate after the dissolution removal step to perform wet wettability uniformization treatment; a mask blank forming step of forming a mask blank by forming a metal thin film on at least one surface of the regenerated glass substrate for a photomask; a resist forming step of forming a resist in a pattern on the metal thin film; and an etching step of etching the exposed portion of the metal thin film on which the resist is formed.
According to this aspect, by having the above-described regeneration treatment step, even when a regenerated glass substrate is used, a photomask having a metal thin film with a good pattern shape can be produced while preventing peeling of the metal thin film.
In this embodiment, the steps and other matters except the regeneration treatment step may be the same as those described in the above-mentioned "1. 1 st embodiment", and therefore, the description thereof will be omitted here.
The regenerating treatment step in this embodiment may be the same as that described in the above "method for manufacturing a regenerated glass substrate for photomask", and therefore, a description thereof will be omitted here.
The present invention is not limited to the above embodiments. The above-described embodiments are merely exemplary, and any embodiments having substantially the same configuration as the technical idea described in the claims of the present invention and exhibiting the same operational effects are included in the technical scope of the present invention.
Examples
[ example 1]
Hereinafter, examples of the present invention were subjected to a regeneration treatment using a photomask of synthetic quartz glass having a glass substrate size of 450mm × 550mm and a thickness of 5mm for a liquid crystal panel.
The used photomask was completely removed of the chromium film by a chromium etching solution, and was washed with pure water to prepare a glass blank. In this state, the expired air image was checked, and as a result, the removed original pattern trace was confirmed.
Subsequently, the regenerated substrate from which the chromium film was removed was immersed in a 5% KOH aqueous solution at a liquid temperature of 25 ℃ for 4 hours, and then washed with pure water. The glass etching amount was 0.6 μm, and the substrate thus washed was subjected to a breath image inspection, whereby a photomask glass substrate in which the original pattern had disappeared and the pattern could not be visually checked was obtained.
Next, a chrome blank substrate for a photomask was used in which a pure chrome film was formed on the main surface of the regenerated glass substrate using a vacuum sputtering film-forming apparatus, and then a chrome oxide film was formed thereon.
The surface of the chromium blank substrate was visually inspected, and the original pattern was not confirmed.
Further, a photomask was produced in the same manner as in the photomask production process described above, and as a result, a photomask was obtained which was free from any dimensional abnormality, white defects unique to a regenerated substrate, or the like.
[ example 2]
A regeneration treatment of the photomask manufactured in the same manner as in example 1 was performed.
After the photomask is used, the photomask is subjected to a regeneration process for reuse as a photomask substrate.
The used photomask was completely removed of the chromium film by a chromium etching solution, and was washed with pure water to prepare a glass blank. In this state, the expired air image was checked, and as a result, the removed original pattern trace was confirmed.
Subsequently, the regenerated substrate from which the chromium film was removed was immersed in a 10% KOH aqueous solution at a liquid temperature of 25 ℃ for 4 hours, and then washed with pure water. The glass etching amount was 1.5 μm, and as a result of the breath image inspection of the cleaned substrate, a photomask glass substrate in which the original pattern had disappeared and the pattern could not be visually checked was obtained.
Next, a chrome blank substrate for a photomask was used in which a pure chrome film was formed on the main surface of the regenerated glass substrate using a vacuum sputtering film-forming apparatus, and then a chrome oxide film was formed thereon. The surface of the chromium blank substrate was visually inspected, and as a result, no original pattern was observed.
Further, a photomask was produced in the same manner as in the photomask production process described above, and as a result, a photomask was obtained which was free from any dimensional abnormality, white defects unique to a regenerated substrate, or the like.
[ example 3]
A regeneration treatment of the photomask manufactured in the same manner as in example 1 was performed.
After the photomask is used, the photomask is subjected to a regeneration process for reuse as a photomask substrate.
The used photomask was completely removed of the chromium film by a chromium etching solution, and was washed with pure water to prepare a glass blank. In this state, the expired air image was checked, and as a result, the removed original pattern trace was confirmed.
Next, the regenerated substrate from which the chromium film was removed was immersed in the solution 3 at a liquid temperature of 25 ℃ for 4 hours, and washed with pure water. The glass etching amount is 1 μm or less, and the washed substrate is subjected to a breath image inspection, whereby a photomask glass substrate in which the original pattern is lost and the pattern cannot be confirmed by visual inspection can be obtained.
Next, a chrome blank substrate for a photomask was used in which a pure chrome film was formed on the main surface of the regenerated glass substrate using a vacuum sputtering film-forming apparatus, and then a chrome oxide film was formed thereon.
The surface of the chromium blank substrate was visually inspected, and as a result, no original pattern was observed.
Further, a photomask was produced in the same manner as in the photomask production process described above, and as a result, a photomask was obtained which was free from any dimensional abnormality, white defects unique to a regenerated substrate, or the like.
[ comparative example ]
A regeneration treatment of the photomask manufactured in the same manner as in example 1 was performed.
In the same manner as in example 1, the chromium film was completely removed by the chromium etching solution, and the glass blank was prepared by washing with pure water. In this state, the reproduced glass substrate was subjected to a breath image test, and as a result, the removed original pattern trace was confirmed.
A chrome blank substrate for a photomask was used, in which a pure chrome film was formed on the main surface of the regenerated glass substrate by a vacuum sputtering film-forming apparatus and then a chrome oxide film was formed thereon. The surface of the chromium blank substrate was visually inspected, and as a result, no original pattern was observed.
Further, a photomask is produced in the same manner as in the photomask production process, and as a result, a large number of white defects unique to the regenerated substrate are generated.
Description of the symbols
1 glass substrate for photomask
2 chromium film part
Chrome part in 2a photomask state
2a portion after 2b chromium film etching treatment
3 chromium film image part
Image part in 3a photomask state
3a portion after 3b chromium film etching treatment
Part of W immersed in the wettability equalizing treatment liquid
White defect
Claims (8)
1. A glass substrate for a photomask, which is a glass substrate obtained by regenerating a photomask having a metal thin film pattern formed on at least one surface of a glass substrate,
on the glass substrate, a metal thin film formed as a photomask is dissolved and removed by an etching solution,
and wet-wetting homogenization treatment is carried out on the glass substrate until the pattern does not appear in the breath image inspection,
the etching solution is ammonium ceric nitrate, perchloric acid or nitric acid.
2. The glass substrate for a photomask according to claim 1, wherein the wet wettability equalizing treatment and the breath image inspection are repeatedly performed.
3. The glass substrate for a photomask according to claim 1 or 2, wherein the wettability of the surface of the glass substrate for a photomask is uniformized by the wet wettability uniformizing treatment.
4. The glass substrate for a photomask according to claim 1 or 2, wherein the wet wettability equalizing treatment is a treatment with an alkaline aqueous solution.
5. The glass substrate for a photomask according to claim 4, wherein the alkali component of the alkaline aqueous solution is potassium hydroxide.
6. The glass substrate for a photomask according to claim 1 or 2, wherein the difference in contact angle of water is 1 degree or less on the surface of the glass substrate for a photomask subjected to the regeneration treatment.
7. A photomask blank using the photomask glass substrate according to claim 1 or 2.
8. A photomask using the photomask blank according to claim 7.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012-211636 | 2012-09-26 | ||
| JP2012211636 | 2012-09-26 | ||
| JP2013-116166 | 2013-05-31 | ||
| JP2013116166 | 2013-05-31 | ||
| CN201380047359.8A CN104620176B (en) | 2012-09-26 | 2013-09-19 | Glass regeneration treating method, repeat glass substrate and photomask blank and photomask using it |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201380047359.8A Division CN104620176B (en) | 2012-09-26 | 2013-09-19 | Glass regeneration treating method, repeat glass substrate and photomask blank and photomask using it |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109298594A CN109298594A (en) | 2019-02-01 |
| CN109298594B true CN109298594B (en) | 2021-12-24 |
Family
ID=50388105
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811229615.6A Active CN109298594B (en) | 2012-09-26 | 2013-09-19 | Glass recycling method, recycled glass substrate, and photomask blank and photomask using same |
| CN201380047359.8A Active CN104620176B (en) | 2012-09-26 | 2013-09-19 | Glass regeneration treating method, repeat glass substrate and photomask blank and photomask using it |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201380047359.8A Active CN104620176B (en) | 2012-09-26 | 2013-09-19 | Glass regeneration treating method, repeat glass substrate and photomask blank and photomask using it |
Country Status (5)
| Country | Link |
|---|---|
| JP (2) | JP6256344B2 (en) |
| KR (3) | KR101848983B1 (en) |
| CN (2) | CN109298594B (en) |
| TW (1) | TWI558677B (en) |
| WO (1) | WO2014050700A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104932194A (en) * | 2015-07-22 | 2015-09-23 | 京东方科技集团股份有限公司 | Mask plate, manufacturing method thereof, and recycling method of mask plate |
| CN112404100A (en) * | 2020-11-03 | 2021-02-26 | 福建晶安光电有限公司 | Recovery process of filter substrate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101101440A (en) * | 2006-07-06 | 2008-01-09 | 富士通日立等离子显示器股份有限公司 | Glass mask used for patterning and manufacturing method and apparatus therefor |
| KR20080076807A (en) * | 2007-02-14 | 2008-08-20 | 주식회사 코젝스 | Method for machining glass using a photosensitive resin composition |
| CN101821058A (en) * | 2008-06-11 | 2010-09-01 | 信越化学工业株式会社 | Polishing agent for synthetic quartz glass substrate |
| CN102372424A (en) * | 2010-08-12 | 2012-03-14 | Hoya株式会社 | Substrate for masking base, masking base and method for manufacturing transferring mask |
Family Cites Families (27)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS514754B1 (en) * | 1970-10-28 | 1976-02-14 | ||
| JPS5988332A (en) * | 1982-11-08 | 1984-05-22 | Fujitsu Ltd | Method for regenerating substrate for photomask |
| JPS626259A (en) * | 1985-07-02 | 1987-01-13 | Sharp Corp | Photomask substrate |
| JPH02102142A (en) | 1988-10-07 | 1990-04-13 | Sony Corp | Regeneration of jig made of quartz |
| JPH05143981A (en) * | 1991-11-25 | 1993-06-11 | Kao Corp | Method for cleaning substrate |
| JPH07230081A (en) * | 1994-02-17 | 1995-08-29 | Toppan Printing Co Ltd | Method for recovering glass substrate |
| JPH0839025A (en) * | 1994-07-28 | 1996-02-13 | Olympus Optical Co Ltd | Cleaning method |
| JPH08151599A (en) * | 1994-11-30 | 1996-06-11 | Olympus Optical Co Ltd | Composition for finish washing and method for finish washing |
| JPH09241684A (en) * | 1996-03-04 | 1997-09-16 | Olympus Optical Co Ltd | Cleaning composition and cleaning method |
| JPH11172148A (en) * | 1997-12-12 | 1999-06-29 | Kobe Steel Ltd | Hydrophilic coating material and production of hydrophilic substrate |
| JP4035251B2 (en) * | 1999-02-03 | 2008-01-16 | 株式会社神戸製鋼所 | Substrate having surface hydrophilicity and method for producing the same |
| KR20010068561A (en) * | 2000-01-06 | 2001-07-23 | 윤여선 | Mask recycle process |
| US20040137828A1 (en) * | 2002-07-17 | 2004-07-15 | Hoya Corporation | Glass substrate for a mask blank, method of producing a glass substrate for a mask blank, mask blank, method of producing the mask blank, transfer mask, and method of producing a transfer mask |
| JP3764734B2 (en) * | 2002-07-17 | 2006-04-12 | Ｈｏｙａ株式会社 | Manufacturing method of mask blanks |
| JP2004089807A (en) * | 2002-08-30 | 2004-03-25 | Central Glass Co Ltd | Cleaning devices and cleaning method |
| DE102004014954A1 (en) * | 2003-03-27 | 2005-03-10 | Hoya Corp | Method for producing a glass substrate for a mask blank and method for producing a mask blank |
| JP4497909B2 (en) * | 2003-12-16 | 2010-07-07 | Ｈｏｙａ株式会社 | Method for regenerating glass substrate for mask blank, method for manufacturing mask blank, and method for manufacturing transfer mask |
| JP2007069339A (en) * | 2005-09-09 | 2007-03-22 | Sharp Corp | Removing method of membrane on front surface of substrate |
| CN102681332B (en) * | 2006-05-30 | 2015-03-11 | Hoya株式会社 | Resist film peeling method, mask blank manufacturing method and transfer mask manufacturing method |
| JP2008151916A (en) * | 2006-12-15 | 2008-07-03 | Shin Etsu Chem Co Ltd | Method for recycling large-size photomask substrate |
| KR101243545B1 (en) * | 2008-08-04 | 2013-03-20 | 도판 인사츠 가부시키가이샤 | Apparatus for reclaiming glass substrate |
| JP5569000B2 (en) | 2010-01-20 | 2014-08-13 | 大日本印刷株式会社 | Method for generating glass substrate for photomask |
| JP5578708B2 (en) * | 2010-04-19 | 2014-08-27 | Ｈｏｙａ株式会社 | Reproduction photomask substrate production method for FPD production, reproduction photomask blank production method, reproduction photomask production method with pellicle, and pattern transfer method |
| JP2012022124A (en) * | 2010-07-14 | 2012-02-02 | Toppan Printing Co Ltd | Photomask blank, photo mask and substrate reproduction method |
| JP5635839B2 (en) * | 2010-08-31 | 2014-12-03 | Hoya株式会社 | Mask blank substrate manufacturing method and mask blank manufacturing method |
| JP2013178371A (en) * | 2012-02-28 | 2013-09-09 | Hoya Corp | Method for removing thin film of substrate with thin film, method for manufacturing transfer mask, method for regenerating substrate and method for manufacturing mask blank |
| JP6210270B2 (en) * | 2013-05-14 | 2017-10-11 | 株式会社ニコン | Surface treatment method for glass substrate and photomask regeneration method |
-
2013
- 2013-09-19 WO PCT/JP2013/075314 patent/WO2014050700A1/en active Application Filing
- 2013-09-19 KR KR1020157005441A patent/KR101848983B1/en active IP Right Grant
- 2013-09-19 CN CN201811229615.6A patent/CN109298594B/en active Active
- 2013-09-19 JP JP2014538440A patent/JP6256344B2/en active Active
- 2013-09-19 KR KR1020187034398A patent/KR102085058B1/en active IP Right Grant
- 2013-09-19 KR KR1020177031593A patent/KR101963996B1/en active IP Right Grant
- 2013-09-19 CN CN201380047359.8A patent/CN104620176B/en active Active
- 2013-09-26 TW TW102134718A patent/TWI558677B/en active
-
2017
- 2017-12-07 JP JP2017234845A patent/JP2018045253A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101101440A (en) * | 2006-07-06 | 2008-01-09 | 富士通日立等离子显示器股份有限公司 | Glass mask used for patterning and manufacturing method and apparatus therefor |
| KR20080076807A (en) * | 2007-02-14 | 2008-08-20 | 주식회사 코젝스 | Method for machining glass using a photosensitive resin composition |
| CN101821058A (en) * | 2008-06-11 | 2010-09-01 | 信越化学工业株式会社 | Polishing agent for synthetic quartz glass substrate |
| CN102372424A (en) * | 2010-08-12 | 2012-03-14 | Hoya株式会社 | Substrate for masking base, masking base and method for manufacturing transferring mask |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2014050700A1 (en) | 2016-08-22 |
| TW201427918A (en) | 2014-07-16 |
| KR101963996B1 (en) | 2019-03-29 |
| CN104620176A (en) | 2015-05-13 |
| CN104620176B (en) | 2019-02-26 |
| JP2018045253A (en) | 2018-03-22 |
| TWI558677B (en) | 2016-11-21 |
| KR20150050557A (en) | 2015-05-08 |
| KR101848983B1 (en) | 2018-04-13 |
| KR102085058B1 (en) | 2020-03-05 |
| KR20180129996A (en) | 2018-12-05 |
| KR20170125119A (en) | 2017-11-13 |
| CN109298594A (en) | 2019-02-01 |
| JP6256344B2 (en) | 2018-01-10 |
| WO2014050700A1 (en) | 2014-04-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8252488B2 (en) | Mask blank substrate manufacturing method, and reflective mask blank manufacturing method | |
| CN106933026B (en) | Photomask, photomask substrate, method for manufacturing photomask substrate, photomask blank, and method for manufacturing display device | |
| JP5578708B2 (en) | Reproduction photomask substrate production method for FPD production, reproduction photomask blank production method, reproduction photomask production method with pellicle, and pattern transfer method | |
| JP4974389B2 (en) | Pellicle frame for lithography and pellicle for lithography | |
| CN109298594B (en) | Glass recycling method, recycled glass substrate, and photomask blank and photomask using same | |
| CN111679551B (en) | Dustproof film assembly | |
| JP4688966B2 (en) | Mask blank manufacturing method and transfer mask manufacturing method | |
| JP2012022124A (en) | Photomask blank, photo mask and substrate reproduction method | |
| TWI408509B (en) | Photomask mounting/housing device and resist inspection method and resist inspection apparatus using same | |
| KR101838758B1 (en) | A pellicle frame | |
| JPS6344824Y2 (en) | ||
| JP2005202135A (en) | Method for cleaning photomask, method for manufacturing photomask, and method for handling photomask | |
| JP4566547B2 (en) | Mask blank manufacturing method and transfer mask manufacturing method | |
| JP4397596B2 (en) | Photomask manufacturing method | |
| WO2004088421A1 (en) | Mask blank, mask blank manufacturing method, transfer mask manufacturing method, and semiconductor device manufacturing method | |
| JP2010066619A (en) | Pellicle and method for manufacturing the same | |
| CN110928137B (en) | Mask and manufacturing method thereof | |
| JPH03263048A (en) | Method for peeling resist for photomask | |
| JPS6218560A (en) | Photomask blank and photomask | |
| JP6123292B2 (en) | Lithographic original plate cleaning method | |
| JPH04104153A (en) | Manufacture of mask | |
| US20050247807A1 (en) | System for automatically recycling flat glass from workpiece and method of the same | |
| KR20040014377A (en) | Method for making mask or mask blank by using wasted mask | |
| JP2001305718A (en) | Photomask and method for manufacturing semiconductor device | |
| JP2011123155A (en) | Regeneration system for color filter substrate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |