CN109782525B - Mask substrate and method of manufacturing the same, phase shift mask and method of manufacturing the same - Google Patents
Mask substrate and method of manufacturing the same, phase shift mask and method of manufacturing the same Download PDFInfo
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- CN109782525B CN109782525B CN201811051930.4A CN201811051930A CN109782525B CN 109782525 B CN109782525 B CN 109782525B CN 201811051930 A CN201811051930 A CN 201811051930A CN 109782525 B CN109782525 B CN 109782525B
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- 230000010363 phase shift Effects 0.000 title claims abstract description 170
- 239000000758 substrate Substances 0.000 title claims abstract description 75
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 63
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 152
- 239000000126 substance Substances 0.000 claims abstract description 134
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 75
- 238000002310 reflectometry Methods 0.000 claims abstract description 37
- 239000007789 gas Substances 0.000 claims description 72
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 63
- 239000001301 oxygen Substances 0.000 claims description 63
- 229910052760 oxygen Inorganic materials 0.000 claims description 63
- 238000000034 method Methods 0.000 claims description 48
- 230000015572 biosynthetic process Effects 0.000 claims description 33
- 230000003595 spectral effect Effects 0.000 claims description 15
- 229910021332 silicide Inorganic materials 0.000 claims description 6
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 claims description 6
- 239000010410 layer Substances 0.000 description 268
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 53
- 229910016006 MoSi Inorganic materials 0.000 description 36
- 238000004544 sputter deposition Methods 0.000 description 33
- 229910052751 metal Inorganic materials 0.000 description 30
- 239000002184 metal Substances 0.000 description 30
- 239000011521 glass Substances 0.000 description 28
- 238000002834 transmittance Methods 0.000 description 22
- 239000002585 base Substances 0.000 description 21
- 239000000463 material Substances 0.000 description 20
- 229910052710 silicon Inorganic materials 0.000 description 18
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 15
- 239000010703 silicon Substances 0.000 description 15
- 150000002739 metals Chemical class 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- 229910052804 chromium Inorganic materials 0.000 description 9
- 239000011651 chromium Substances 0.000 description 9
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 229910045601 alloy Inorganic materials 0.000 description 7
- 239000000956 alloy Substances 0.000 description 7
- 238000005530 etching Methods 0.000 description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 230000008033 biological extinction Effects 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 239000002356 single layer Substances 0.000 description 5
- 229910052721 tungsten Inorganic materials 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 238000003475 lamination Methods 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000012495 reaction gas Substances 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000005401 electroluminescence Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 229920002120 photoresistant polymer Polymers 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 229910052715 tantalum Inorganic materials 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005137 deposition process Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000001272 nitrous oxide Substances 0.000 description 2
- 238000000059 patterning Methods 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 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 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- -1 MSi Chemical class 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical group [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- SJKRCWUQJZIWQB-UHFFFAOYSA-N azane;chromium Chemical compound N.[Cr] SJKRCWUQJZIWQB-UHFFFAOYSA-N 0.000 description 1
- CXOWYMLTGOFURZ-UHFFFAOYSA-N azanylidynechromium Chemical compound [Cr]#N CXOWYMLTGOFURZ-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- UFGZSIPAQKLCGR-UHFFFAOYSA-N chromium carbide Chemical compound [Cr]#C[Cr]C#[Cr] UFGZSIPAQKLCGR-UHFFFAOYSA-N 0.000 description 1
- 229910021563 chromium fluoride Inorganic materials 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 1
- 150000002222 fluorine compounds Chemical group 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000001449 potential sputter etching Methods 0.000 description 1
- 229910003470 tongbaite Inorganic materials 0.000 description 1
- FTBATIJJKIIOTP-UHFFFAOYSA-K trifluorochromium Chemical compound F[Cr](F)F FTBATIJJKIIOTP-UHFFFAOYSA-K 0.000 description 1
- 238000001039 wet etching Methods 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
-
- 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
- G03F1/52—Reflectors
-
- 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
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/70—Microphotolithographic exposure; Apparatus therefor
- G03F7/70691—Handling of masks or workpieces
-
- 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
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/70—Microphotolithographic exposure; Apparatus therefor
- G03F7/708—Construction of apparatus, e.g. environment aspects, hygiene aspects or materials
- G03F7/7095—Materials, e.g. materials for housing, stage or other support having particular properties, e.g. weight, strength, conductivity, thermal expansion coefficient
- G03F7/70958—Optical materials or coatings, e.g. with particular transmittance, reflectance or anti-reflection properties
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Epidemiology (AREA)
- Public Health (AREA)
- Preparing Plates And Mask In Photomechanical Process (AREA)
- Physical Vapour Deposition (AREA)
Abstract
The invention provides a mask substrate and a manufacturing method thereof, a phase shift mask and a manufacturing method thereof. The mask blank of the present invention is a mask blank having a layer to be a phase shift mask, the mask blank having: a phase shift layer and a low reflectivity layer laminated on the transparent substrate; and a chemical resistance layer which is provided at a position farther from the transparent substrate than the phase shift layer and the low-reflectance layer and which has improved chemical resistance, wherein the nitrogen content in the chemical resistance layer is set to be higher than the nitrogen content in the low-reflectance layer.
Description
Technical Field
The present invention relates to a technique suitable for use in a mask substrate, a phase shift mask, a method for manufacturing a mask substrate, and a method for manufacturing a phase shift mask.
Background
With the high definition of flat panel displays (flat panel display, FPD), the need for forming fine patterns is increasing. Therefore, not only a mask of a light shielding film conventionally used but also an edge-enhanced phase shift mask (PSM mask) is used (see patent document 1).
Such a phase shift mask requires reduced reflectivity.
Patent document 1: re-public table WO2004/070472
Such a phase shift mask preferably reduces reflectance at the time of exposure, and thus a film having a low refractive index needs to be formed on the surface. In order to obtain a film having a low refractive index in the phase shift mask, an oxide film composed of an oxidized metal is preferably used.
On the other hand, in order to remove the contaminant affecting the optical characteristics from the mask, it is necessary to clean the mask using an acidic or basic chemical liquid. It is known that the oxidized metal film has poor resistance to an alkali solution in this cleaning step.
However, it is known that a metal film used for a phase shift mask has a relationship between promotion of oxidation of the film and resistance to an alkali solution (chemical liquid resistance).
In the phase shift mask, it is required to realize a phase shift film having a small reflectance and a high chemical liquid resistance.
Disclosure of Invention
The present invention has been made in view of the above circumstances, and an object of the present invention is to realize a phase shift film having both a small reflectance and a strong chemical liquid resistance.
The mask blank according to the first aspect of the present invention solves the above-described problems by the following means. A mask substrate having a layer that becomes a phase shift mask, the mask substrate having: a phase shift layer and a low reflectivity layer laminated on the transparent substrate; and a chemical resistance layer which is provided at a position farther from the transparent substrate than the phase shift layer and the low-reflectance layer and which has improved chemical resistance, wherein the nitrogen content in the chemical resistance layer is set to be higher than the nitrogen content in the low-reflectance layer.
In the mask blank according to the first aspect of the present invention, the oxygen content of the low-reflectivity layer is preferably set to be higher than the oxygen content of the chemical-resistant layer.
As for the mask base according to the first aspect of the present invention, in the chemical resistant layer and the low-reflectance layer, the spectral reflectance may have a profile protruding downward in the vicinity of the wavelength 400 nm.
In the mask blank according to the first aspect of the present invention, the refractive index of the low-reflectivity layer at the wavelength of 405nm may be set to 2.2 or less.
In the mask blank according to the first aspect of the present invention, the refractive index of the chemical-resistant layer at the wavelength of 405nm may be set to 2.4 or more.
In addition, in the mask base according to the first aspect of the present invention, the chemical resistant layer and the low-reflectivity layer may be composed of silicide.
In the mask blank according to the first aspect of the present invention, the nitrogen content of the chemical resistant layer may be 36atm% or more.
In the mask blank according to the first aspect of the present invention, the low-reflectivity layer may have a nitrogen content of 35atm% or less and an oxygen content of 30atm% or more.
In the mask blank according to the first aspect of the present invention, the chemical resistant layer may have a film thickness of 15nm or less.
In the mask blank according to the first aspect of the present invention, the refractive index of the phase shift layer at the wavelength of 405nm may be set to 2.4 or more.
In the mask blank according to the first aspect of the present invention, the nitrogen content of the phase shift layer may be 36atm% or more.
A phase shift mask according to a second aspect of the present invention is manufactured using the mask blank according to the first aspect.
A method for manufacturing a mask blank according to a third aspect of the present invention is the method for manufacturing a mask blank according to the first aspect, wherein the partial pressure of nitrogen is different between the chemical resistant layer and the low-reflectivity layer during the formation of the chemical resistant layer.
In the method for manufacturing a mask blank according to the third aspect of the present invention, partial pressures of the oxygen-containing gas may be different from each other at the time of forming the chemical resistant layer and the low-reflectivity layer.
In the method for manufacturing a phase shift mask according to the fourth aspect of the present invention, in the method for manufacturing a phase shift mask according to the second aspect, the nitrogen partial pressure may be different from each other when the chemical resistant layer and the low-reflectivity layer are formed.
In the method for manufacturing a phase shift mask according to the fourth aspect of the present invention, partial pressures of the oxygen-containing gas may be different from each other at the time of forming the chemical resistant layer and the low-reflectivity layer.
A mask blank according to a first aspect of the present invention is a mask blank having a layer to be a phase shift mask, the mask blank including: a phase shift layer and a low reflectivity layer laminated on the transparent substrate; and a chemical resistance layer which is provided at a position farther from the transparent substrate than the phase shift layer and the low-reflectance layer and which has improved chemical resistance, wherein the nitrogen content in the chemical resistance layer is set to be higher than the nitrogen content in the low-reflectance layer. Thus, a mask substrate that can be a phase shift mask having the following mask layers can be provided: the mask layer has a reflectance reduced to a predetermined range, and has resistance to chemicals used in a cleaning process and the like and a desired phase shift effect.
Here, as the chemical, an alkaline chemical or an acidic chemical may be used. Examples of the developer, the stripping liquid, and the cleaning liquid include sodium hydroxide (NaOH), potassium hydroxide (KOH), tetramethylammonium hydroxide (TMAH), and sulfuric acid (H) 2 SO 4 ) Sulfuric acid and hydrogen peroxide (H) 2 O 2 ) In particular, sodium hydroxide solution is exemplified.
Further, as the mask base according to the first aspect of the present invention, a large mask used in polychromatic exposure in manufacturing an FPD can be considered.
In the mask blank according to the first aspect of the present invention, the oxygen content of the low-reflectivity layer is set to be higher than the oxygen content of the chemical-resistant layer and the phase shift layer, whereby the reflectivity in the reflectivity layer can be reduced, and the mask layer has low reflectivity and phase shift capability in, for example, a wavelength band from g-line (436 nm) to i-line (365 nm) in a state where a decrease in film thickness due to chemicals is prevented by the chemical-resistant layer.
In the case of the mask base according to the first aspect of the present invention, in the chemical resistant layer and the low-reflectance layer, the spectral reflectance has a profile protruding downward in the vicinity of 400 nm. Thus, a low reflectance required as a mask can be achieved in a wavelength region of exposure light used in an exposure apparatus such as a step beam splitter.
In the mask blank according to the first aspect of the present invention, the low reflectance layer may have a refractive index of 2.2 or less at a wavelength of 405nm, thereby realizing the low reflectance.
In the mask blank according to the first aspect of the present invention, the refractive index of the chemical-resistant layer at the wavelength of 405nm is set to 2.4 or more. Thus, as a film used as a phase shift mask, it is possible to have a necessary low reflectance and chemical resistance.
In the mask blank according to the first aspect of the present invention, the chemical resistant layer and the low-reflectivity layer are made of silicide. Thus, a film having a predetermined phase shift capability and a high chemical liquid resistance can be obtained.
Thus, the silicide film that can be suitably used as a phase mask is not limited to MoSi-based materials composed of Mo and Si, and metal and silicon (MSi, M: mo, ni, W, zr, ti, cr, or other transition metals), oxidized and nitrided Metal and Silicon (MSiON), oxidized and carbonized Metal and Silicon (MSiCO), oxidized, nitrided, and carbonized Metal and Silicon (MSiCON), oxidized Metal and Silicon (MSiO), nitrided Metal and Silicon (MSiN), and the like may be cited, and metal such as Ta, ti, W, mo or Zr, alloys of these metals with each other, alloys of these metals with other metals (Cr or Ni may be cited as other metals), or materials containing these metals or alloys with silicon may be cited. Particularly, moSi films can be cited.
In the mask blank according to the first aspect of the present invention, the nitrogen content of the chemical resistant layer is 36atm% or more, whereby a desired chemical resistance can be achieved, and for example, the reflectance and the phase shift capability can be prevented from deviating from the previously set ranges by suppressing the film thickness fluctuation in the cleaning step.
In the mask blank according to the first aspect of the present invention, the low reflectance layer has a nitrogen content of 35atm% or less and an oxygen content of 30atm% or more, whereby a low reflectance can be set within a predetermined range.
In the mask blank according to the first aspect of the present invention, the chemical resistant layer has a film thickness of 15nm or less, whereby the desired chemical resistance can be achieved and the reflectance set by the low reflectance layer can be prevented from deviating from the originally set range.
In the mask blank according to the first aspect of the present invention, the refractive index of the phase shift layer at the wavelength of 405nm is set to 2.4 or more, whereby a desired phase shift capability can be provided.
In the mask blank according to the first aspect of the present invention, the phase shift layer may have a nitrogen content of 36atm% or more, thereby providing a desired phase shift capability.
In addition, since the phase shift mask according to the second aspect of the present invention is manufactured using the mask blank according to the first aspect, it is possible to have a desired phase shift capability with a chemical resistance and a low reflectance.
A method for manufacturing a mask blank according to a third aspect of the present invention is the method for manufacturing a mask blank according to the first aspect, wherein the partial pressure of nitrogen is different between the chemical resistant layer and the low-reflectivity layer during the formation of the chemical resistant layer. Thus, by forming the chemical resistant layer and the low reflectance layer at a predetermined nitrogen content, a mask substrate having predetermined film characteristics can be manufactured.
In the method for manufacturing a mask blank according to the third aspect of the present invention, partial pressures of oxygen-containing gases are different from each other at the time of forming the chemical resistant layer and the low-reflectivity layer. Thus, by forming the chemical resistant layer and the low reflectance layer at a predetermined oxygen content, a mask substrate having predetermined film characteristics can be manufactured.
In addition, a method for manufacturing a phase shift mask according to a fourth aspect of the present invention is the method for manufacturing a phase shift mask according to the second aspect, wherein the nitrogen partial pressure is different between the chemical resistant layer and the low-reflectivity layer during the formation of the chemical resistant layer. Thus, a phase shift mask having desired film characteristics for each layer can be manufactured.
In the method for manufacturing a phase shift mask according to the fourth aspect of the present invention, partial pressures of oxygen-containing gas are made different from each other at the time of forming the chemical resistant layer and the low-reflectivity layer. Thus, a phase shift mask having desired film characteristics for each layer can be manufactured.
The mode of the invention can bring the following effects: namely, a mask substrate and a phase shift mask having chemical resistance and low reflectivity and having a predetermined phase shift property can be provided.
Drawings
Fig. 1 is a cross-sectional view showing a mask blank according to a first embodiment of the present invention.
Fig. 2 is a cross-sectional view showing a phase shift mask according to a first embodiment of the present invention.
Fig. 3 is a schematic view showing a film forming apparatus in a method for manufacturing a mask blank and a phase shift mask according to a first embodiment of the present invention.
Fig. 4 is a schematic view showing a film forming apparatus in a method for manufacturing a mask blank and a phase shift mask according to a first embodiment of the present invention.
Fig. 5 is a graph showing N showing a transmittance change after NaOH treatment in the mask blank, the phase shift mask, the method for manufacturing the mask blank, and the method for manufacturing the phase shift mask according to the first embodiment of the present invention 2 Graph of Ar gas ratio dependence.
Fig. 6 is a graph showing the nitrogen concentration dependence of the transmittance change after NaOH treatment in the mask blank, the phase shift mask, the method for manufacturing the mask blank, and the method for manufacturing the phase shift mask according to the first embodiment of the present invention.
FIG. 7 shows a mask blank, a phase shift mask, and a mask blank according to a first embodiment of the present inventionCO of which transmittance after NaOH treatment varies in the method for manufacturing a phase shift mask 2 Graph of concentration dependence.
Fig. 8 is a graph showing the wavelength dependence of refractive index in the mask blank, the phase shift mask, the method for manufacturing the mask blank, and the method for manufacturing the phase shift mask according to the first embodiment of the present invention.
Fig. 9 is a graph showing the wavelength dependence of the extinction coefficient in the mask blank, the phase shift mask, the method for manufacturing the mask blank, and the method for manufacturing the phase shift mask according to the first embodiment of the present invention.
Fig. 10 is a graph showing a relationship between a spectral reflectance and film thickness characteristics of a chemical resistant layer/a low reflectance layer in the mask base, the phase shift mask, the method for manufacturing the mask base, and the method for manufacturing the phase shift mask according to the first embodiment of the present invention.
Fig. 11 is a graph showing a relationship between a spectral reflectance and film thickness characteristics of a chemical resistant layer/a low reflectance layer in the mask base, the phase shift mask, the method for manufacturing the mask base, and the method for manufacturing the phase shift mask according to the first embodiment of the present invention.
Detailed Description
Next, a mask blank, a phase shift mask, a method for manufacturing a mask blank, and a method for manufacturing a phase shift mask according to a first embodiment of the present invention will be described with reference to the drawings.
Fig. 1 is a cross-sectional view showing a mask substrate in the present embodiment, and fig. 2 is a cross-sectional view showing a phase shift mask in the present embodiment, in which reference numeral 10B is a mask substrate.
The mask blank 10B according to the present embodiment is provided to a phase shift mask used in a range of 365nm to 436nm as an exposure light. As shown in fig. 1, the mask base 10B is configured of a glass substrate 11 (transparent substrate), a phase shift layer 12 formed on the glass substrate 11, a low-reflectivity layer 13 formed on the phase shift layer 12, and a chemical resistant layer 14 formed on the low-reflectivity layer 13. These phase shift layer 12, low reflectance layer 13 and chemical resistant layer 14 constitute a low reflectance phase shift film as a mask layer.
The mask base 10B according to the present embodiment may have a structure in which a protective layer, a light shielding layer, a resist layer, and the like are laminated in addition to the phase shift layer 12, the low reflectance layer 13, and the chemical resistant layer 14.
As the transparent substrate 11, a material excellent in transparency and optical isotropy can be used, and for example, a quartz glass substrate can be used. The size of the transparent substrate 11 is not particularly limited, and may be appropriately selected according to a substrate (for example, a substrate for an FPD such as an LCD (liquid crystal display), a plasma display, or an organic EL (electro luminescence) display) to be exposed using the mask.
Examples of the phase shift layer 12 and the chemical resistant layer 14 include a silicide film containing nitrogen, for example, a film containing a metal such as Ta, ti, W, mo or Zr, or an alloy containing such a metal and silicon, particularly a MoSiX (x.gtoreq.2) film (for example, moSi) 2 Film, MOSi 3 Film or MoSi 4 Films, etc.).
As the low-reflectance layer 13, a silicide film containing nitrogen may be used as the phase shift layer 12 and the chemical resistant layer 14, but an oxygen-containing film may also be used.
As a result of intensive studies, the present inventors have found that, regarding the composition of MoSi films, the higher the Mo ratio in the composition ratio of Mo and Si, the higher the metallic properties of MoSi films, and therefore the wavelength dependence of transmittance decreases. From this, it is understood that the value of X in the MoSiX film is preferably 3 or less, and the value of X is more preferably 2.5 or less. Thus, a target with an X value of 2.3 was used in this study.
In this embodiment, the nitrogen content (nitrogen concentration) of the phase shift layer 12 is preferably 36atm% or more, and the nitrogen concentration of the phase shift layer 12 is more preferably 40atm% or more.
The nitrogen concentration of the low-reflectance layer 13 is preferably 35atm% or less, and the nitrogen concentration of the low-reflectance layer 13 is more preferably 30atm% or less.
The nitrogen concentration of the chemical resistant layer 14 is preferably 36atm% or more, more preferably 40atm% or more, and the film thickness of the chemical resistant layer 14 is preferably 20nm or less, more preferably 15nm or less. The film thickness of the chemical resistant layer 14 may be 0nm or more, and preferably 5nm or more.
Meanwhile, in the present embodiment, the oxygen content (oxygen concentration) of the low-reflectance layer 13 is preferably 25atm% or more, and the oxygen content of the low-reflectance layer 13 is more preferably 30atm% or more.
At this time, the oxygen concentration of the phase shift layer 12 may be 7.0 to 10atm%, and the oxygen concentration of the chemical resistant layer 14 may be 7.0 to 10atm%.
In the method for manufacturing the mask base according to the present embodiment, after the phase shift layer 12 is formed on the glass substrate 11 (transparent substrate), the low reflectance layer 13 and the chemical resistant layer 14 are formed.
In the case of laminating a protective layer, a light shielding layer, an antireflection layer, a resist layer, and the like in addition to the phase shift layer 12, the low reflectance layer 13, and the chemical resistance layer 14, the mask base manufacturing method may have a lamination process of these layers.
As an example, a light-shielding layer containing chromium is given.
As shown in fig. 2, the phase shift mask 10 in the present embodiment can be obtained by forming patterns on the phase shift layer 12, the low reflectance layer 13, and the chemical resistant layer 14 of the mask substrate 10B.
Next, a method for manufacturing the phase shift mask 10 from the mask base 10B according to the present embodiment will be described.
A photoresist layer is formed on the outermost surface of the mask substrate 10B. The photoresist layer may be either positive or negative. The photoresist layer may use a liquid resist.
Next, a resist pattern is formed on the outside of the chemical resistant layer 14 by exposing and developing the resist layer. The resist pattern functions as an etching mask for the phase shift layer 12, the low reflectance layer 13, and the chemical resistant layer 14, and the shape is appropriately determined according to the etching patterns of the phase shift layer 12, the low reflectance layer 13, and the chemical resistant layer 14. As an example, in the phase shift field, a shape having an opening width corresponding to the opening width dimension of the phase shift pattern to be formed is set.
Next, the phase shift layer 12, the low reflectance layer 13, and the chemical resistant layer 14 are wet etched with an etching solution through the resist pattern to form phase shift patterns 12P, 13P, 14P. In the case where the phase shift layer 12, the low reflectance layer 13, and the chemical resistant layer 14 are MoSi, it is preferable to use an etching solution containing at least one fluorine compound selected from hydrofluoric acid, and ammonium bifluoride and at least one oxidizing agent selected from hydrogen peroxide, nitric acid, and sulfuric acid as the etching solution.
Further, in the case where the mask base 10B is configured by forming another film such as a light shielding layer, a pattern having a predetermined shape corresponding to the phase shift patterns 12P, 13P, and 14P is formed on the film by wet etching or the like using a corresponding etching solution. Patterning of other films such as the light shielding layer may be performed by a predetermined process before and after patterning of the phase shift layer 12, the low reflectance layer 13, and the chemical resistant layer 14 in accordance with the lamination order.
The phase shift mask 10 having the phase shift patterns 12P, 13P, 14P as shown in fig. 2 is obtained through the above steps.
Next, a method for manufacturing a mask base in this embodiment mode will be described with reference to the drawings.
Fig. 3 is a schematic view showing an apparatus for manufacturing a mask blank according to the present embodiment, and fig. 4 is a schematic view showing an apparatus for manufacturing a mask blank according to the present embodiment.
The mask blank 10B in the present embodiment is manufactured by the manufacturing apparatus shown in fig. 3 or 4.
The manufacturing apparatus S10 shown in fig. 3 is a reciprocating sputtering apparatus, and includes a loading and unloading chamber S11 and a film forming chamber S12 (vacuum processing chamber) connected to the loading and unloading chamber S11 through a sealing portion S13.
The loading and unloading chamber S11 is provided with a conveyor S11a for conveying the glass substrate 11, which is conveyed from the outside, to the film forming chamber S12 or to the outside of the film forming chamber S12, and an exhaust device S11b such as a rotary pump for evacuating the interior of the loading and unloading chamber S11.
The film forming chamber S12 is provided with a substrate holding device S12a, a cathode electrode S12c (backing plate) having a target S12b functioning as a supply portion for supplying a film forming material, a power source S12d for applying a negative potential sputtering voltage to the backing plate S12c, a gas introduction device S12e for introducing a gas into the film forming chamber S12, and a high vacuum exhaust device S12f such as a turbo molecular pump for evacuating the interior of the film forming chamber S12.
The substrate holding device S12a can hold the glass substrate 11 conveyed by the conveying device S11a so that the glass substrate 11 faces the target S12b during film formation, and can convey the glass substrate 11 from the loading and unloading chamber S11 into and out of the loading and unloading chamber S11.
The target S12b is made of a material having a composition necessary for forming a film on the glass substrate 11.
In the manufacturing apparatus S10 shown in fig. 3, the glass substrate 11 is carried into the manufacturing apparatus S10 through the loading and unloading chamber S11. Thereafter, the glass substrate 11 is formed by sputtering in a film forming chamber S12 (vacuum processing chamber). Thereafter, the glass substrate S11 having finished film formation is carried out from the loading and unloading chamber S11 to the outside of the manufacturing apparatus S10.
In the film forming step, a sputtering gas and a reaction gas are supplied from the gas introduction device S12e to the film forming chamber S12, and a sputtering voltage is applied from an external power source to the backing plate S12c (cathode electrode). The target S12b may be formed with a predetermined magnetic field by a magnetron magnetic circuit. In the film forming chamber S12, ions of the sputtering gas excited by the plasma collide with the target S12b of the cathode electrode S12c, and particles of the film forming material are flown out. The flying particles are bonded to the reaction gas and then attached to the glass substrate 11, whereby a predetermined film is formed on the surface of the glass substrate 11.
At this time, in the process of forming the phase shift layer 12, the chemical resistant layer 14, and the low reflectance layer 13, different amounts of nitrogen gas and oxygen-containing gas are supplied from the gas introduction device S12e, and the amounts of the gases are changed to control the partial pressure of the gases, so that the compositions of the phase shift layer 12, the chemical resistant layer 14, and the low reflectance layer 13 are set within the set ranges.
Here, CO is exemplified as the oxygen-containing gas 2 (carbon dioxide), O 2 (oxygen, N) 2 O (nitrous oxide) and NO (nitric oxide), etc.
In the deposition process of the phase shift layer 12, the chemical resistant layer 14, and the low reflectance layer 13, the target S12b may be replaced if necessary.
Further, a laminated film may be formed on the phase shift layer 12, the low reflectance layer 13, and the chemical resistant layer 14, in addition to the film formation. In this case, the sputtering conditions of the target, the gas, and the like used for forming the laminated film may be adjusted, the laminated film may be formed by sputtering, and other film forming methods may be used. The mask base 10B according to the present embodiment is obtained by forming a laminated film in this manner.
The manufacturing apparatus S20 shown in fig. 4 is an in-line sputtering apparatus. The sputtering apparatus includes a loading chamber S21, a film forming chamber S22 (vacuum processing chamber) connected to the loading chamber S21 via a sealing portion S23, and an unloading chamber S25 connected to the film forming chamber S22 via a sealing portion S24.
The loading chamber S21 is provided with a conveyor S21a for conveying the glass substrate 11 carried in from the outside to the film forming chamber S22, and an exhaust device S21b such as a rotary pump for evacuating the interior of the loading chamber S21.
The film forming chamber S22 is provided with a substrate holding device S22a, a cathode electrode S22c (backing plate) having a target S22b functioning as a supply portion for supplying a film forming material, a power source S22d for applying a negative sputtering voltage to the backing plate S22c, a gas introduction device S22e for introducing a gas into the film forming chamber S22, and a high vacuum exhaust device S22f such as a turbo molecular pump for evacuating the interior of the film forming chamber S22.
The substrate holding device S22a holds the glass substrate 11 conveyed by the conveying device S21a so that the glass substrate 11 faces the target S22b during film formation. Further, the substrate holding device S22a can carry the glass substrate 11 in from the loading chamber S21 and out to the unloading chamber S25.
The target S22b is made of a material having a composition necessary for forming a film on the glass substrate 11.
The unloading chamber S25 is provided with a conveyor S25a for conveying the glass substrate 11 carried in from the film forming chamber S22 to the outside, and an exhaust device S25b such as a rotary pump for evacuating the interior of the unloading chamber S25.
In the manufacturing apparatus S20 shown in fig. 4, the glass substrate 11 is carried into the manufacturing apparatus S20 through the loading chamber S21. Thereafter, the glass substrate 11 is formed by sputtering in a film forming chamber S22 (vacuum processing chamber). Thereafter, the glass substrate 11 having been film-formed is carried out from the unloading chamber S25 to the outside of the manufacturing apparatus S20.
In the film forming step, a sputtering gas and a reaction gas are supplied from a gas introduction device S22e to the film forming chamber S22, and a sputtering voltage is applied from an external power source to the backing plate S22c (cathode electrode). In addition, a predetermined magnetic field may be formed on the target S22b by a magnetron magnetic circuit. In the film forming chamber S22, ions of the sputtering gas excited by the plasma collide with the target S22b of the cathode electrode S22c, and particles of the film forming material are flown out. The flying particles are bonded to the reaction gas and then attached to the glass substrate 11, whereby a predetermined film is formed on the surface of the glass substrate 11.
At this time, in the process of forming the phase shift layer 12, the chemical resistant layer 14, and the low reflectance layer 13, different amounts of nitrogen gas and oxygen-containing gas are supplied from the gas introduction device S22e, and the amounts of the gases are changed to control the partial pressure of the gases, so that the compositions of the phase shift layer 12, the chemical resistant layer 14, and the low reflectance layer 13 are set within the set ranges.
Here, CO is exemplified as the oxygen-containing gas 2 (carbon dioxide), O 2 (oxygen, N) 2 O (nitrous oxide) or NO (nitric oxide), etc.
In the deposition process of the phase shift layer 12, the chemical resistant layer 14, and the low reflectance layer 13, the target S22b may be replaced if necessary.
Further, a laminated film may be formed on the phase shift layer 12, the chemical resistant layer 14, and the low reflectance layer 13, as well as on these layers. In this case, the sputtering conditions of the target, the gas, and the like used for forming the laminated film may be adjusted, the laminated film may be formed by sputtering, and other film forming methods may be used. The mask base 10B according to the present embodiment is obtained by forming a laminated film in this manner.
Next, film characteristics of the phase shift layer 12, the low reflectance layer 13, and the chemical resistant layer 14 in this embodiment will be described.
Here, for the sake of explanation, the phase shift layer 12, the low reflectance layer 13, and the chemical resistant layer 14 are assumed to be films made of MoSi, but are not limited thereto.
In the phase shift layer 12, the low reflectance layer 13, and the chemical resistant layer 14 which are the low reflection phase shift film according to the present embodiment, the nitrogen concentration in the low reflectance layer 13 is set lower than the nitrogen concentration of the phase shift layer 12 and the chemical resistant layer 14.
Specifically, by changing N at the time of film formation based on sputtering 2 The low reflectance layer 13 is formed into a MoSi film having a nitrogen concentration of 30% or less.
By varying N at the time of film formation based on sputtering 2 The partial pressure is, for example, a MoSi film having a nitrogen concentration of 40% or more formed on the chemical resistant layer 14.
By varying N at the time of film formation based on sputtering 2 The partial pressure is, for example, moSi film having a nitrogen concentration of 40% or more formed on the phase shift layer 12. In order to function the phase shift layer 12 as a necessary phase shifter, the phase shift layer 12 may have a different partial pressure of nitrogen than the chemical resistant layer 14.
In addition, in the phase shift layer 12, the low reflectance layer 13, and the chemical resistant layer 14 which are the low reflection phase shift film according to the present embodiment, the oxygen concentration in the low reflectance layer 13 is set higher than the oxygen concentration in the phase shift layer 12 and the chemical resistant layer 14.
Specifically, by changing CO as an oxygen-containing gas at the time of film formation by sputtering 2 The partial pressure is, for example, a MoSi film having an oxygen concentration of 30% or more formed by forming the low reflectance layer 13.
By varying CO as an oxygen-containing gas in the formation of a film by sputtering 2 The partial pressure is, for example, a MoSi film having an oxygen concentration of 30% or less formed on the chemical resistant layer 14.
By varying CO as an oxygen-containing gas in the formation of a film by sputtering 2 The partial pressure is, for example, moSi film having an oxygen concentration of 30% or less, formed on the phase shift layer 12. In order to function the phase shift layer 12 as a necessary phase shifter, the phase shift layer 12 may be set to have a different partial pressure of the oxygen-containing gas than the chemical resistant layer 14.
Here, film property changes due to nitrogen and oxygen content changes were verified.
First, the transmittance change due to the nitrogen content change was verified. As an example, N in the case of changing the film formation by sputtering is shown in table 1 2 The composition ratio of the MoSi film monolayer varies in the case of partial pressure.
TABLE 1
As shown in table 1, it is understood that when the composition ratio of nitrogen is changed, the transmittance is changed. In the phase shift layer 12, the low reflectance layer 13, and the chemical resistant layer 14 which are the low reflection phase shift film according to the present embodiment, it is possible to set the phase shift film to have a predetermined transmittance by using this case.
Next, chemical resistance due to the change in nitrogen content was verified.
FIG. 5 is a graph showing N showing a change in transmittance after NaOh treatment in the low reflection phase shift film according to the present embodiment 2 FIG. 6 is a graph showing the dependence of nitrogen concentration on the transmittance change after NaOH treatment in the low-reflection phase-shift film according to the present embodiment, and FIG. 7 is a graph showing the transmittance change after NaOH treatment in the low-reflection phase-shift film according to the present embodiment 2 Graph of concentration dependence.
As an example, in the case of sputtering based and by changing N 2 The transmittance change at 405nm before and after alkali lye treatment was examined in the single layer of the MoSi film formed by partial pressure of gas.
The process conditions here are as follows: the concentration of NaOH is 5%, the temperature is 40 ℃, and the soaking time is changed within 15-60 minutes. In addition, as the gas conditions at the time of film formation, the same as N in Table 1 2 The partial pressure correspondingly shows N 2 Ar flow ratio.
From the results, the following dependence of nitrogen partial pressure was found: as shown in fig. 5 and 6, when the nitrogen partial pressure is changed from 100% to 0%, the transmittance at 405nm changes greatly as the nitrogen partial pressure becomes smaller according to the film thickness change after NaOH treatment.
Therefore, the following film thickness variations and nitrogen concentration dependence were found: in the case where the nitrogen concentration is 40atm% or more, the transmittance change at 405nm is almost negligible.
Next, the cause of CO is validated 2 Chemical resistance due to the change in partial pressure of gas.
As an example, table 2 shows CO at the time of changing film formation by sputtering 2 The composition ratio of the MoSi film monolayer varies in the case of partial pressure. Here, N 2 Partial pressure and Ar partial pressure were 10:0, CO only 2 The partial pressure was varied in the flow rate of 1 to 10 sccm.
TABLE 2
Next, based on sputtering and by varying CO 2 The transmittance change at 405nm before and after alkali lye treatment was examined in the single layer of the MoSi film formed by partial pressure of gas.
The process conditions here are as follows: the concentration of NaOH is 5%, the temperature is 40 ℃, and the soaking time is changed within 15-60 minutes.
From this result, the following oxygen dependence was found: as shown in FIG. 7, the CO is only used in the process of 2 When the partial pressure of the gas is changed within the flow rate of 1 to 10sccm, the partial pressure of the gas is changed according to the film thickness after NaOH treatment, and the partial pressure of the gas is changed according to CO 2 The gas flow amount becomes large, and the transmittance change at 405nm becomes large.
Therefore, the following film thickness changes and oxygen concentration dependence were found: in the case where the oxygen concentration in the chemical resistant layer 14 is small, the transmittance change at 405nm is almost negligible.
Next, the wavelength dependence was verified.
Fig. 8 is a graph showing the wavelength dependence of refractive index in the phase shift film according to the present embodiment, and fig. 9 is a graph showing the wavelength dependence of extinction coefficient in the phase shift film according to the present embodiment.
As an example, in the case of sputtering based and by changing CO 2 The wavelength dependence of refractive index and extinction coefficient was examined in the single layer of MoSi film formed by partial pressure of gas.
From the results, it is understood that the catalyst has the following CO 2 Gas flow dependence: as shown in FIG. 8, in CO 2 In the case of changing the gas flow rate from 1sccm to 10sccm, the flow rate was changed with CO 2 The gas flow amount becomes large, the refractive index change at each wavelength becomes small, and the extinction coefficient becomes small as shown in fig. 9.
Next, the spectral reflectance change was verified.
Fig. 10 is a graph showing the relationship between the spectral reflectance and the film thickness characteristics of the chemical resistant layer/low reflectance layer in the phase shift film according to the present embodiment, and fig. 11 is a graph showing the relationship between the spectral reflectance and the film thickness characteristics of the chemical resistant layer/low reflectance layer in the phase shift film according to the present embodiment.
As an example, in the low reflectance layer 13 and the chemical resistant layer 14 made of MoSi, the film thickness dependence of the spectral reflectance at 405nm was examined when the film thickness of the chemical resistant layer 14 was changed to 0nm to 20nm and the film thickness of the low reflectance layer 13 was changed to 0nm or 40 nm.
The results are shown in fig. 10.
A is shown in the figure; film thickness of chemical resistant layer/B; low reflectivity layer film thickness.
In addition, the nitrogen concentration in the low reflectance layer 13 at this time was 29.5atm% (N at the time of film formation) 2 The gas partial pressure was 30%), the oxygen concentration in the low reflectance layer 13 was 23.0atm% (CO at the time of film formation) 2 The gas flow rate was 5 sccm), the nitrogen concentration in the chemical-resistant layer 14 was 49.9atm% (N at the time of film formation) 2 Partial pressure of 100%) and oxygen concentration in the chemical-resistant layer 14 was 9.9atm% (CO at the time of film formation 2 The gas flow rate was 0 sccm).
In the lamination of these MoSi films, the gas may be continuously supplied while changing only the nitrogen concentration, or the nitrogen component of the supplied gas may be changed at the time of lamination to a predetermined film thickness as a different sputtering stepPressure and CO 2 Gas flow rate.
From the results, it is understood that in the chemical resistant layer 14 and the low reflectance layer 13, the spectral reflectance has a profile protruding downward in the vicinity of 400nm at various film thicknesses.
Here, the wavelength at which the reflectance profile protrudes downward can be set in a range from around 400nm to around 500nm by changing the film thicknesses of the chemical resistant layer 14 and the low reflectance layer 13.
Similarly, in the low reflectance layer 13 and the chemical resistant layer 14 made of MoSi, the film thickness dependence of the spectral reflectance at 405nm was examined when the film thickness of the chemical resistant layer 14 was changed to 0nm to 20nm and the film thickness of the low reflectance layer 13 was changed to 0nm to 55 nm.
The results are shown in fig. 11.
A is shown in the figure; film thickness of chemical resistant layer/B; low reflectivity layer film thickness.
In addition, the nitrogen concentration in the low reflectance layer 13 at this time was 29.5atm% (N at the time of film formation) 2 The gas partial pressure was 30%), the oxygen concentration in the low reflectance layer 13 was 23.0atm% (CO at the time of film formation) 2 The gas flow rate was 5 sccm), the nitrogen concentration in the chemical-resistant layer 14 was 49.9atm% (N at the time of film formation) 2 Partial pressure of 100%) and oxygen concentration in the chemical-resistant layer 14 was 9.9atm% (CO at the time of film formation 2 The gas flow rate was 0 sccm).
From this result, in the chemical resistant layer 14 and the low reflectance layer 13, the spectral reflectance has a profile protruding downward in the vicinity of 400nm at various film thicknesses, and it is possible to set the wavelengths at which the reflectance profile protrudes downward to be concentrated in the vicinity of 400nm by setting the film thicknesses of the chemical resistant layer 14 and the low reflectance layer 13.
As described above, it is understood that the reflectance can be reduced in a desired wavelength region by using the embodiment of the present invention.
In the present embodiment, when the phase shift layer 12, the low reflectance layer 13, and the chemical resistant layer 14 are formed of MoSi, the N is controlled by controlling 2 Partial pressure and CO 2 Partial pressure and film thickness are controlled to produce a low reflection phase shift film having low reflectance and high chemical resistanceIs provided, the phase shift mask 10 is provided.
Moreover, the mask substrate 10B and the phase shift mask 10 can be manufactured as follows: when the mask substrate 10B and the phase shift mask 10 are cleaned with an acidic or basic chemical in order to remove contaminants affecting the optical characteristics in the cleaning step, the mask substrate 10B and the phase shift mask 10 have high resistance, and the film thickness variation and the accompanying variation in reflectance and transmittance are small.
In the mask base 10B and the phase shift mask 10 for manufacturing the FPD device according to the present embodiment, N at the time of film formation is changed and controlled for the phase shift layer 12, the low reflectance layer 13, and the chemical resistant layer 14 made of MoSi as the low reflection phase shift film 2 Partial pressure and CO 2 Partial pressure and film thickness. By only such control, it is possible to control the peak value (the downward convex outline of fig. 10 and 11) of the most reducible reflectivity among the phase shift layer 12, the low reflectivity layer 13, and the chemical resistant layer 14 made of MoSi in at least the band from the i-line to the g-line and the vicinity thereof emitted from the ultra-high pressure mercury lamp to be in the vicinity of 405 nm. Thus, a phase shifter having a phase shift capability and capable of reducing the reflectance in a predetermined band may be used.
In the mask base 10B and the phase shift mask 10 for manufacturing the FPD device according to the present embodiment, the materials of the phase shift layer 12, the low reflectance layer 13, and the chemical resistant layer 14, which are the low reflection phase shift film, are not limited to the MoSi-based materials composed of Mo and Si. Examples of the material include metal and silicon (transition metal such as MSi, M: mo, ni, W, zr, ti, and Cr), oxidized and nitrided Metal and Silicon (MSiON), oxidized and carbonized Metal and Silicon (MSiCO), oxidized, nitrided and carbonized Metal and Silicon (MSiCON), oxidized Metal and Silicon (MSiO), and nitrided Metal and Silicon (MSiN). Further, metals such as Ta, ti, W, mo and Zr, alloys of these metals or alloys of these metals with other metals (Cr or Ni is exemplified as the other metals), and materials containing these metals or alloys and silicon are exemplified.
The mask substrate 10B and the phase shift mask 10 for manufacturing the FPD device according to the present embodiment may have a light shielding layer. In this case, for example, the material of the light shielding layer is preferably a material having etching characteristics different from those of the low reflection phase shift film, and in the case where the metal constituting the low reflection phase shift film is molybdenum, the material of the light shielding layer is preferably chromium, an oxide of chromium, a nitride of chromium, a carbide of chromium, a fluoride of chromium, or a material containing at least one of them. Similarly, in the case where the semipermeable membrane is made of a chromium nitride film-based material, the material of the light shielding layer is preferably chromium, chromium oxide, chromium nitride, chromium carbide, chromium fluoride, or a material containing at least one of them.
The light shielding layer may be formed by a top-mounted structure in which the light shielding layer is disposed on the outer side of the low reflection phase shift film with respect to the glass substrate 11, or a bottom-mounted structure in which the light shielding layer is disposed on the inner side of the low reflection phase shift film. Further, a resist layer may be provided between the light shielding layer and the low reflection phase shift film at this time.
The mask base 10B and the phase shift mask 10 for manufacturing the FPD device according to the present embodiment can be manufactured by changing only the nitrogen concentration and the oxygen concentration of the phase shift layer 12, the low reflectance layer 13, and the chemical resistant layer 14, which are low reflection phase shift films. Thus, the mask base 10B and the phase shift mask 10 can be manufactured by supplying only the atmosphere gas which is set in advance to a predetermined concentration (predetermined flow rate ratio) at the time of sputtering. This makes it possible to easily make the nitrogen concentration and the oxygen concentration uniform in the in-plane direction of the low reflection phase shift film, and to suppress variations in the reflectance, transmittance, and phase shift capability in the in-plane direction.
In the present embodiment, the phase shift layer 12, the low-reflectivity layer 13, and the chemical resistant layer 14 may have a structure in which the nitrogen concentration and the oxygen concentration are changed in the film thickness direction. In this case, if a high nitrogen concentration is maintained in the outermost surface (outer position) in order to maintain chemical resistance, the film thickness and nitrogen concentration and oxygen concentration can be appropriately changed so as to maintain a prescribed reflectance, transmittance and phase shift capability.
Examples (example)
The following describes embodiments of the present invention.
Example 1 ]
On a large glass substrate (composite) using a large in-line sputtering apparatusQuartz (QZ): 10mm thick and 850mm x 1200mm in size) was used for forming the low reflection phase shift mask. Specifically, using a MoSiX target having an X value of 2.3, ar gas and N 2 The gas serves as a sputtering gas to form a MoSi film. At this time, a plurality of samples were produced by changing the nitrogen partial pressure as shown in table 1 and changing the nitrogen concentration stepwise to 44.9atm% (experimental example 1), 40.8atm% (experimental example 2), 29.5atm% (experimental example 3) and 7.2atm% (experimental example 4).
The films of experimental examples 1 to 4 were examined for the change in transmittance at 405nm before and after NaOH treatment, and the results are shown in fig. 5 and 6.
The process conditions here are as follows: the concentration of NaOH is 5%, the temperature is 40 ℃, and the soaking time is changed within 15-60 minutes. In addition, as the gas conditions at the time of film formation, the same as N in Table 1 2 The partial pressure correspondingly shows N 2 Ar flow ratio.
Example 2 ]
Next, ar gas and N were mixed in the same manner as in the above-mentioned experimental examples 1 to 4 2 Gas and CO 2 The gas was used as a sputtering gas to form a MoSi film. At this time, CO is changed as shown in FIG. 7 2 The gas flow rate was changed stepwise to 9.9atm% (example 5), 12.7atm% (example 6), 18.0atm% (example 7), 34.7atm% (example 8) and 47.1atm% (example 9) in oxygen concentration, thereby producing a plurality of samples.
The films of experimental examples 5 to 9 were examined for the change in transmittance at 405nm before and after the NaOH treatment, and the results are shown in fig. 7.
Here, the processing conditions were as follows, in the same manner as in the above-described experimental examples 1 to 4: the concentration of NaOH is 5%, the temperature is 40 ℃, and the soaking time is changed within 15-60 minutes. In addition, as the gas conditions at the time of film formation, the same as N in Table 1 2 The partial pressure correspondingly shows N 2 Ar flow ratio.
Further, the films of experimental examples 5 to 9 were examined for the wavelength dependence of refractive index and extinction coefficient, and the results are shown in fig. 8 and 9.
From these results, it is understood that chemical resistance and transmittance and refractive index vary according to the oxygen concentration in the MoSi film.
Next, in order to investigate CO as an oxygen-containing film forming gas 2 The films of examples 5 to 9 were analyzed for the composition ratio of C (carbon) in the gas. The results are shown in table 3.
TABLE 3
From these results and data, it is understood that the carbon concentration does not have a great influence on the chemical resistance. Further, it is known that even if carbon is contained, the film can function as an antireflection film.
Example 3]
Next, as in example 2, three layers of a MoSi film having a nitrogen concentration of 49.5atm% and an oxygen concentration of 6.69atm%, a MoSi film having a nitrogen concentration of 29.5atm% and an oxygen concentration of 36.77atm%, and a MoSi film having a nitrogen concentration of 49.5atm% and an oxygen concentration of 6.69atm% were laminated in the film thickness direction. In this case, in order to make the nitrogen concentration of the layer on the glass substrate side high and the oxygen concentration low, after the MoSi film is formed to a predetermined film thickness after the film formation is started, the N of the introduced gas is changed 2 Partial pressure of gas and CO 2 Partial pressure of gas and with N at the uppermost layer 2 The film formation was performed by increasing the nitrogen partial pressure so that the gas partial pressure concentration had the chemical resistance in example 2.
In addition, in the state after stacking MoSi films having different nitrogen concentrations and oxygen concentrations, when the film thickness of the uppermost high nitrogen concentration film was a and the film thickness of the second high oxygen concentration MoSi film was B, a/B was changed to 0nm/0nm (example 10), 0nm/40nm (example 11), 5nm/40nm (example 12), 10nm/40nm (example 13), 15nm/40nm (example 14), and 20nm/40nm (example 15).
The films of the above experimental examples 10 to 15 were examined for the wavelength dependence of the spectral reflectance, and the results are shown in fig. 10.
Similarly, when the film thickness of the uppermost high nitrogen concentration film was A and the film thickness of the second high oxygen concentration MoSi film was B in a state where the MoSi films having different nitrogen concentrations and oxygen concentrations were stacked, A/B was changed to 0nm/0nm (example 10), 0nm/40nm (example 11), 5nm/35nm (example 16), 10nm/30nm (example 17), 15nm/15nm (example 18) and 20nm/10nm (example 19).
The films of the above experimental examples 10, 11, and 16 to 19 were examined for the wavelength dependence of the spectral reflectance, and the results are shown in fig. 11.
From these results, it is understood that the profile of the spectral reflectance in the laminated film is projected downward for the film thickness of the uppermost high nitrogen concentration film by changing the nitrogen concentration and the oxygen concentration in the MoSi film in the thickness direction and adjusting the film thickness thereof.
Here, by changing the nitrogen concentration and the oxygen concentration in the MoSi film in the thickness direction, the wavelength at which the profile of the reflectance protrudes downward can be set in a range from around 400nm to around 500 nm.
Further, by changing the nitrogen concentration and the oxygen concentration in the MoSi film in the thickness direction and adjusting the film thickness, it is possible to set the wavelength at which the profile of the reflectance protrudes downward to be concentrated around 400 nm.
It is thus understood that the reflectivity can be reduced in a desired wavelength region by using the phase shift mask of the present invention.
Industrial applicability
As an application example of the present invention, the present invention can be applied to all masks required in the manufacture of an LCD or an organic EL display. For example, the present invention can be applied to masks for manufacturing TFTs, color filters, or the like.
Description of the reference numerals
10 … phase shift mask
10B … mask substrate
11 … glass substrate (transparent substrate)
12 … phase shift layer
13 … low reflectivity layer
14 … chemical resistant layer
12P, 13P, 14P … phase shift pattern
S10, S20 … film Forming apparatus (sputtering apparatus)
S11 … loading and unloading chamber
S21 … loading chamber
S25 … unloader
S11a, S21a, S25a … conveyor (conveyor robot)
S11b, S21b, S25b … exhaust device
S12, S22 … film forming chamber (Chamber)
S12a, S22a … substrate holding device
S12b, S22b … target
S12c, S22c … back plate (cathode electrode)
S12d and S22d … power supply
S12e and S22e … gas introduction device
S12f and S22f ….
Claims (15)
1. A mask substrate having a layer that becomes a phase shift mask, the mask substrate having:
a phase shift layer and a low reflectivity layer laminated on the transparent substrate; and
A chemical resistance layer which is provided at a position farther from the transparent substrate than the phase shift layer and the low reflectance layer and which has improved chemical resistance,
the nitrogen content in the chemical resistant layer is set to be higher than the nitrogen content of the low reflectivity layer,
the refractive index of the low-reflectivity layer at a wavelength of 405nm is set to 2.2 or less.
2. The mask blank according to claim 1,
the oxygen content of the low-reflectivity layer is set to be higher than the oxygen content of the chemical-resistant layer.
3. The mask blank according to claim 1 or 2,
in the chemical resistant layer and the low reflectance layer, the spectral reflectance has a profile protruding downward in the vicinity of a wavelength of 400 nm.
4. The mask blank according to claim 1 or 2,
the refractive index of the chemical resistant layer at a wavelength of 405nm is set to 2.4 or more.
5. The mask blank according to claim 1 or 2,
the chemical resistant layer and the low reflectivity layer are comprised of a silicide.
6. The mask blank according to claim 1 or 2,
the nitrogen content of the chemical resistant layer is 36atm% or more.
7. The mask blank according to claim 1 or 2,
the low-reflectivity layer has a nitrogen content of 35atm% or less and an oxygen content of 30atm% or more.
8. The mask blank according to claim 1 or 2,
the chemical resistant layer has a film thickness of 15nm or less.
9. The mask blank according to claim 1 or 2,
the refractive index of the phase shift layer at a wavelength of 405nm is set to 2.4 or more.
10. The mask blank according to claim 1 or 2,
the nitrogen content of the phase shift layer is 36atm% or more.
11. A phase shift mask fabricated using the mask substrate of any one of claims 1 to 10.
12. A method of manufacturing a mask substrate, comprising,
the mask blank according to any one of claims 1 to 10,
the nitrogen partial pressures are made different from each other at the time of film formation of the chemical resistant layer and the low reflectance layer.
13. The method for manufacturing a mask substrate according to claim 12,
the partial pressures of the oxygen-containing gas are made different from each other at the time of film formation of the chemical resistant layer and the low reflectance layer.
14. A method of manufacturing a phase shift mask,
the phase shift mask is the phase shift mask of claim 11,
the nitrogen partial pressures are made different from each other at the time of film formation of the chemical resistant layer and the low reflectance layer.
15. The method for manufacturing a phase shift mask according to claim 14,
The partial pressures of the oxygen-containing gas are made different from each other at the time of film formation of the chemical resistant layer and the low reflectance layer.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017219236A JP6998181B2 (en) | 2017-11-14 | 2017-11-14 | Mask blank, phase shift mask and its manufacturing method |
| JP2017-219236 | 2017-11-14 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109782525A CN109782525A (en) | 2019-05-21 |
| CN109782525B true CN109782525B (en) | 2023-10-27 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811051930.4A Active CN109782525B (en) | 2017-11-14 | 2018-09-10 | Mask substrate and method of manufacturing the same, phase shift mask and method of manufacturing the same |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP6998181B2 (en) |
| KR (1) | KR20190054905A (en) |
| CN (1) | CN109782525B (en) |
| TW (1) | TWI767053B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7254599B2 (en) * | 2019-04-15 | 2023-04-10 | アルバック成膜株式会社 | Method for manufacturing mask blanks and method for manufacturing phase shift mask |
| JP7303077B2 (en) * | 2019-09-10 | 2023-07-04 | アルバック成膜株式会社 | Method for manufacturing mask blanks, method for manufacturing photomask, mask blanks and photomask |
| JP7381374B2 (en) * | 2020-03-16 | 2023-11-15 | アルバック成膜株式会社 | Mask blanks, phase shift masks, manufacturing methods |
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Also Published As
| Publication number | Publication date |
|---|---|
| CN109782525A (en) | 2019-05-21 |
| TWI767053B (en) | 2022-06-11 |
| JP6998181B2 (en) | 2022-02-04 |
| JP2019090910A (en) | 2019-06-13 |
| KR20190054905A (en) | 2019-05-22 |
| TW201923119A (en) | 2019-06-16 |
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