CN118625588A - Mask blank, transfer mask, method for manufacturing transfer mask, and method for manufacturing display device - Google Patents
Mask blank, transfer mask, method for manufacturing transfer mask, and method for manufacturing display device Download PDFInfo
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- CN118625588A CN118625588A CN202410233460.2A CN202410233460A CN118625588A CN 118625588 A CN118625588 A CN 118625588A CN 202410233460 A CN202410233460 A CN 202410233460A CN 118625588 A CN118625588 A CN 118625588A
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- film
- mask
- pattern
- thin film
- transfer
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- 238000012546 transfer Methods 0.000 title claims abstract description 176
- 238000000034 method Methods 0.000 title claims abstract description 100
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 71
- 239000010409 thin film Substances 0.000 claims abstract description 249
- 239000000758 substrate Substances 0.000 claims abstract description 102
- 238000000862 absorption spectrum Methods 0.000 claims abstract description 56
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 42
- 239000010703 silicon Substances 0.000 claims abstract description 42
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 35
- 150000003624 transition metals Chemical class 0.000 claims abstract description 35
- 239000010408 film Substances 0.000 claims description 373
- 238000005530 etching Methods 0.000 claims description 135
- 238000010521 absorption reaction Methods 0.000 claims description 79
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 75
- 238000000059 patterning Methods 0.000 claims description 71
- 239000011651 chromium Substances 0.000 claims description 32
- 229910052757 nitrogen Inorganic materials 0.000 claims description 31
- 239000010936 titanium Substances 0.000 claims description 28
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 25
- 229910052804 chromium Inorganic materials 0.000 claims description 25
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 23
- 229910052719 titanium Inorganic materials 0.000 claims description 23
- 238000001039 wet etching Methods 0.000 claims description 10
- 230000007261 regionalization Effects 0.000 abstract description 151
- 238000002834 transmittance Methods 0.000 description 73
- 239000007789 gas Substances 0.000 description 61
- 230000000052 comparative effect Effects 0.000 description 50
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 37
- 238000004544 sputter deposition Methods 0.000 description 34
- 230000010363 phase shift Effects 0.000 description 33
- 230000008569 process Effects 0.000 description 31
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 30
- 239000000463 material Substances 0.000 description 28
- 239000000203 mixture Substances 0.000 description 26
- 230000015572 biosynthetic process Effects 0.000 description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 15
- 229910052786 argon Inorganic materials 0.000 description 15
- 238000005477 sputtering target Methods 0.000 description 14
- 230000008859 change Effects 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 229910021350 transition metal silicide Inorganic materials 0.000 description 12
- 150000004767 nitrides Chemical class 0.000 description 11
- 230000003287 optical effect Effects 0.000 description 11
- 229910021341 titanium silicide Inorganic materials 0.000 description 11
- 239000010453 quartz Substances 0.000 description 10
- 239000002131 composite material Substances 0.000 description 9
- 238000002056 X-ray absorption spectroscopy Methods 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 239000010410 layer Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 238000005546 reactive sputtering Methods 0.000 description 8
- 239000011521 glass Substances 0.000 description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- 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 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 6
- 229920002120 photoresistant polymer Polymers 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000011261 inert gas Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229910001507 metal halide Inorganic materials 0.000 description 5
- 150000005309 metal halides Chemical class 0.000 description 5
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 4
- CXOWYMLTGOFURZ-UHFFFAOYSA-N azanylidynechromium Chemical compound [Cr]#N CXOWYMLTGOFURZ-UHFFFAOYSA-N 0.000 description 4
- 230000000903 blocking effect Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 description 3
- 238000004380 ashing Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- UFGZSIPAQKLCGR-UHFFFAOYSA-N chromium carbide Chemical compound [Cr]#C[Cr]C#[Cr] UFGZSIPAQKLCGR-UHFFFAOYSA-N 0.000 description 3
- 229910000423 chromium oxide Inorganic materials 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 229910003470 tongbaite Inorganic materials 0.000 description 3
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 239000005354 aluminosilicate glass Substances 0.000 description 2
- -1 chromium oxide nitride Chemical class 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 2
- 239000012788 optical film Substances 0.000 description 2
- 238000000206 photolithography Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 239000005361 soda-lime glass Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- SJKRCWUQJZIWQB-UHFFFAOYSA-N azane;chromium Chemical compound N.[Cr] SJKRCWUQJZIWQB-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical compound O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001845 chromium compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000002003 electron diffraction Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 229910052743 krypton Inorganic materials 0.000 description 1
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- FXNGWBDIVIGISM-UHFFFAOYSA-N methylidynechromium Chemical compound [Cr]#[C] FXNGWBDIVIGISM-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000851 scanning transmission electron micrograph Methods 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 230000005469 synchrotron radiation Effects 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
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
- G03F1/50—Mask blanks not covered by G03F1/20 - G03F1/34; Preparation thereof
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
- G03F1/68—Preparation processes not covered by groups G03F1/20 - G03F1/50
- G03F1/80—Etching
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Preparing Plates And Mask In Photomechanical Process (AREA)
- Physical Vapour Deposition (AREA)
Abstract
The invention provides a mask plate, a transfer mask, a method for manufacturing the transfer mask and a method for manufacturing a display device, which meet the requirement of high light resistance for exposure light with wavelength including ultraviolet region. A mask plate is provided with a thin film for pattern formation on a light-transmitting substrate, wherein the thin film contains a transition metal and silicon, and an X-ray absorption spectrum of the thin film obtained by an X-ray absorption spectrum method has a front-side structure in a range of 400-402 eV of the incident energy of X-rays.
Description
Technical Field
The invention relates to a mask blank, a transfer mask, a method for manufacturing a transfer mask, and a method for manufacturing a display device.
Background
In recent years, display devices such as FPDs (FLAT PANEL DISPLAY) including Organic LIGHT EMITTING diodes (Organic light emitting diodes) have been rapidly developed to have a large screen, a wide viewing angle, flexibility such as folding, and high definition and high speed display. One of the elements required for the high definition and high speed display is to manufacture an electronic circuit pattern such as a fine element and wiring having high dimensional accuracy. Patterning of electronic circuits for display devices is often performed by photolithography. Therefore, a transfer mask (photomask) such as a phase shift mask and a binary mask for manufacturing a display device, in which a fine and high-precision pattern is formed, is required.
For example, patent document 1 discloses a photomask for exposing a fine pattern. In the case of the patent document 1, a control unit, such contents are described: a mask pattern formed on a transparent substrate of a photomask is constituted by a light transmitting portion that transmits light of an intensity substantially contributing to exposure and a light semi-transmitting portion that transmits light of an intensity substantially not contributing to exposure. Patent document 1 describes the following: the phase shift effect is used to cancel light passing through the boundary portion between the light semi-transmitting portion and the light transmitting portion, thereby improving the contrast of the boundary portion. Patent document 1 describes that: in the photomask, the light semi-transmitting portion is constituted by a thin film formed of a substance mainly composed of nitrogen, metal and silicon, and silicon is contained in an amount of 34 to 60 at% as a constituent of the substance constituting the thin film.
Patent document 2 describes a halftone phase shift mask plate used for photolithography. Patent document 2 describes a mask plate including a substrate, an etching stop layer deposited on the substrate, and a phase shift layer deposited on the etching stop layer. Patent document 2 also describes that: using the mask plate, a photomask having a phase shift of approximately 180 degrees and a light transmittance of at least 0.001% at a selected wavelength of less than 500nm can be manufactured.
Prior art literature
Patent literature
Patent document 1: japanese patent No. 2966369
Patent document 2: japanese patent application laid-open No. 2005-522740
Disclosure of Invention
Problems to be solved by the invention
As a transfer mask used in the production of a panel with high definition (1000 ppi or more) in recent years, in order to enable high resolution pattern transfer, a transfer mask is required which is formed with a transfer pattern including a thin film pattern for fine pattern formation having an aperture of 6 μm or less and a line width of 4 μm or less. Specifically, a transfer mask having a transfer pattern including a fine pattern having a diameter or a width of 1.5 μm is required.
On the other hand, a transfer mask obtained by patterning a thin film for pattern formation of a mask plate is repeatedly used for pattern transfer to a transfer object, and therefore, it is desired that light resistance (ultraviolet light resistance) to ultraviolet rays for which actual pattern transfer is assumed is also high.
However, it has been difficult to manufacture a mask plate having a thin film for pattern formation which satisfies the requirement of ultraviolet light resistance (hereinafter, simply referred to as light resistance) for exposure light having a wavelength in the ultraviolet region.
The present invention has been made to solve the above-described problems. That is, an object of the present invention is to provide a mask plate that satisfies the requirement of high light resistance to exposure light having a wavelength in the ultraviolet region.
The present invention also provides a transfer mask having a good transfer pattern, which satisfies the requirement of high light resistance to exposure light having a wavelength in the ultraviolet region, a method for manufacturing the transfer mask, and a method for manufacturing a display device.
Means for solving the problems
As means for solving the above problems, the present invention has the following structure.
(Structure 1) A mask blank comprising a thin film for patterning on a light-transmitting substrate, characterized in that,
The film contains a transition metal and silicon,
The X-ray absorption spectrum of the film obtained by the X-ray absorption spectrum method has a front-side structure in a range of an incident X-ray energy of 400eV to 402 eV.
(Structure 2) the mask blank according to structure 1, wherein the X-ray absorption spectrum of the thin film has an absorption edge in a range of an incident X-ray energy of 403eV or more and 406eV or less.
(Structure 3) the mask blank according to structure 2, wherein when the maximum value of the X-ray absorption coefficient at the structure before the edge is IP and the maximum value of the X-ray absorption coefficient at the absorption edge is IA, the relationship of IA/IP of 1.45 or less is satisfied.
(Structure 4) the mask blank according to structure 1, wherein the thin film further contains nitrogen.
(Structure 5) the mask blank according to structure 1, wherein the thin film contains at least titanium as the transition metal.
(Structure 6) the mask blank according to structure 1, wherein a ratio of a content of the transition metal in the thin film to a total content of the transition metal and silicon is 0.05 or more.
(Structure 7) the mask blank according to structure 1, wherein the thin film is provided with an etching mask film having a different etching selectivity with respect to the thin film.
(Constitution 8) the mask blank according to the constitution 7, wherein the etching mask film contains chromium.
(Structure 9) A transfer mask comprising a film having a transfer pattern formed on a light-transmitting substrate,
The film contains a transition metal and silicon,
The X-ray absorption spectrum of the film obtained by the X-ray absorption spectrum method has a front-side structure in a range of an incident X-ray energy of 400eV to 402 eV.
The transfer mask according to the structure 9, wherein the film has an absorption edge in an X-ray absorption spectrum in a range of an incident X-ray energy of 403eV to 406 eV.
(Configuration 11) the transfer mask according to configuration 10, wherein when the maximum value of the X-ray absorption coefficient at the structure before the edge is IP and the maximum value of the X-ray absorption coefficient at the absorption edge is IA, the relationship of IA/IP of 1.45 or less is satisfied.
(Structure 12) the transfer mask according to structure 9, wherein the film further contains nitrogen.
(Structure 13) the transfer mask according to structure 9, wherein the thin film contains at least titanium as the transition metal.
The transfer mask according to the structure 9, wherein a ratio of a content of the transition metal in the thin film to a total content of the transition metal and silicon is 0.05 or more.
(Structure 15) A method for manufacturing a transfer mask, comprising:
Preparing the mask plate of the structure 7 or 8;
forming a resist film having a transfer pattern on the etching mask film;
wet etching is performed using the resist film as a mask, and a transfer pattern is formed on the etching mask film; and
Wet etching is performed using the etching mask film on which the transfer pattern is formed as a mask, and a transfer pattern is formed on the thin film.
(Structure 16) a method for manufacturing a display device, comprising:
Placing the transfer mask according to any one of the structures 9 to 14 on a mask stage of an exposure apparatus; and
The transfer mask is irradiated with exposure light, and a transfer pattern is transferred to a resist film provided on a substrate for a display device.
Effects of the invention
According to the present invention, a mask plate satisfying the requirement of high light resistance to exposure light having a wavelength in the ultraviolet region can be provided.
Further, according to the present invention, it is possible to provide a transfer mask having a good transfer pattern, which satisfies the requirement of high light resistance to exposure light having a wavelength in the ultraviolet region, a method for manufacturing the transfer mask, and a method for manufacturing a display device.
Drawings
Fig. 1 is a schematic cross-sectional view showing a film structure of a mask blank according to an embodiment of the present invention.
Fig. 2 is a schematic cross-sectional view showing another film structure of a mask blank according to an embodiment of the present invention.
There are.
Fig. 3 is a schematic cross-sectional view showing a process for manufacturing a transfer mask according to an embodiment of the present invention.
Fig. 4 is a schematic cross-sectional view showing another process for manufacturing a transfer mask according to an embodiment of the present invention.
Fig. 5 is a graph showing an X-ray absorption spectrum (horizontal axis: X-ray energy incident on the thin film, vertical axis: X-ray absorption coefficient of the thin film to the X-ray energy) obtained by an X-ray absorption spectrometry for the thin films for patterning of the mask plates of examples 1 to 3 and comparative examples 1 and 2 of the present invention.
Fig. 6 is an enlarged view showing a major part of an X-ray absorption spectrum (horizontal axis: X-ray energy incident on the thin film, vertical axis: X-ray absorption coefficient of the thin film to X-rays of the energy) obtained by an X-ray absorption spectrum method for the thin films for pattern formation of the mask plates of examples 1 to 3 and comparative examples 1 and 2 of the present invention.
Fig. 7 is a graph showing the relationship between IA/IP and transmittance in the thin films for patterning of the mask plates of examples 1 to 3 and comparative examples 1 and 2 according to the present invention.
Description of the reference numerals
10: A mask plate;
20: a light-transmitting substrate;
30: a film for pattern formation;
30a: a thin film pattern;
40: etching the mask film;
40a: a first etching mask film pattern;
40b: a second etching mask film pattern;
50: a first resist film pattern;
60: a second resist film pattern;
100: a transfer mask.
Detailed Description
First, the process of the present invention will be described. The present inventors have conducted intensive studies on the structure of a mask plate satisfying the requirement of high light resistance for exposure light having a wavelength in the ultraviolet region (hereinafter, may be simply referred to as "exposure light").
The inventors of the present invention studied to use a transition metal silicide material containing a transition metal and silicon as a material for a thin film pattern of a transfer mask for manufacturing a display device such as an FPD (FLAT PANEL DISPLAY: flat panel display). The following is: in a thin film formed using a transition metal silicide material, there are cases where a large difference in light resistance to exposure light occurs although the composition is substantially the same. Accordingly, the present inventors have variously verified the difference between a thin film of a transition metal silicide material having high light resistance to exposure light and a thin film of a transition metal silicide material having low light resistance to exposure light. First, the inventors of the present invention studied the relationship between the composition of a film and the light resistance to exposure light, but did not obtain a clear relationship between the composition of a film and the light resistance. Further, although observation of a cross-sectional SEM image, a plane STEM image, and an electron diffraction image were performed, no clear correlation was obtained between the light resistance and the SEM image.
Accordingly, the inventors of the present invention focused on the gas composition used in forming the thin film. When a thin film of a transition metal silicide material is formed on a light-transmitting substrate, a sputtering method is generally used. When a thin film of a transition metal silicide material is formed by sputtering, a reactive gas and a rare gas are generally flowed into a film formation chamber.
The inventors of the present invention have further studied intensively, and as a result, have found that, in a transition metal silicide material film having a greatly different light resistance to exposure light having a wavelength in the ultraviolet region, an X-ray absorption spectrum (horizontal axis: X-ray energy incident to a thin film (incident X-ray energy), and vertical axis: X-ray absorption coefficient of the thin film to the X-ray energy) is obtained by an X-ray absorption spectrum method, and as a result, there is a clear difference in the trend of the X-ray absorption coefficient between the two in the X-ray absorption spectrum in the range of the incident X-ray energy originating from nitrogen in a reactive gas. More specifically, it was found that: in a transition metal silicide material film having excellent light resistance to exposure light having a wavelength in an ultraviolet region, an incident X-ray Absorption energy (a range of from 403eV to 406 eV) which is a peak having a large X-ray Absorption coefficient, is present in front of an incident X-ray Absorption energy (a range of from 400eV to 402 eV), and a structure (pre-edge) which is a peak having a small X-ray Absorption coefficient is present.
The mask plate of the present invention was derived by the above intensive studies. Specifically, the mask blank of the present invention is a mask blank comprising a thin film for patterning on a light-transmitting substrate, wherein the thin film contains a transition metal and silicon, and an X-ray absorption spectrum of the thin film obtained by an X-ray absorption spectrum method has a front-side structure in a range of 400eV to 402eV inclusive of an incident energy of X-rays.
Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. The following embodiments are modes for embodying the present invention, and do not limit the scope of the present invention.
Fig. 1 is a schematic diagram showing a film structure of a mask blank 10 of the present embodiment. The mask 10 shown in fig. 1 includes a light-transmissive substrate 20, a thin film 30 (e.g., a phase shift film) for pattern formation formed on the light-transmissive substrate 20, and an etching mask film (e.g., a light shielding film) 40 formed on the thin film 30 for pattern formation.
Fig. 2 is a schematic diagram showing a film structure of a mask plate 10 according to another embodiment. The mask 10 shown in fig. 2 includes a light-transmissive substrate 20 and a thin film 30 (e.g., a phase shift film) for forming a pattern formed on the light-transmissive substrate 20.
In the present specification, the "thin film 30 for pattern formation" refers to a thin film (hereinafter, may be simply referred to as "thin film 30") such as a light shielding film and a phase shift film, in which a predetermined fine pattern is formed in the transfer mask 100. In the description of the present embodiment, a phase shift film is sometimes used as a specific example of the thin film 30 for pattern formation, and a phase shift film pattern is sometimes used as a specific example of the thin film pattern 30a for pattern formation (hereinafter, may be simply referred to as "thin film pattern 30 a"). The light shielding film and light shielding film pattern, the film 30 for forming other patterns such as the transmittance adjustment film and the transmittance adjustment film pattern, and the film pattern 30a for forming the pattern are similar to those of the phase shift film and the phase shift film pattern.
Hereinafter, the light-transmitting substrate 20, the thin film 30 for pattern formation (e.g., a phase shift film), and the etching mask film 40 constituting the mask sheet 10 for manufacturing a display device according to the present embodiment will be described in detail.
< Light-transmitting substrate 20 >)
The light-transmissive substrate 20 is transparent to exposure light. The light-transmitting substrate 20 has a transmittance of 85% or more, preferably 90% or more, with respect to exposure light when no surface reflection loss is present. The light-transmitting substrate 20 is made of a material containing silicon and oxygen, and may be made of a glass material such as synthetic quartz glass, aluminosilicate glass, soda lime glass, or low thermal expansion glass (SiO 2-TiO2 glass, etc.). When the light-transmissive substrate 20 is made of low thermal expansion glass, the positional change of the thin film pattern 30a due to thermal deformation of the light-transmissive substrate 20 can be suppressed. The light-transmitting substrate 20 used for the display device is generally a rectangular substrate. Specifically, a substrate having a length of 300mm or more of the short side of the main surface (surface on which the thin film 30 for pattern formation is formed) of the light-transmissive substrate 20 may be used. In the mask blank 10 of the present embodiment, a large-sized light-transmitting substrate 20 having a length of 300mm or more of the short side of the main surface can be used. Using the mask blank 10 of the present embodiment, a transfer mask 100 having a transfer pattern including, for example, a thin film pattern 30a for forming a fine pattern having a width dimension and/or a diameter dimension of less than 2.0 μm on the light-transmissive substrate 20 can be manufactured. By using the transfer mask 100 according to this embodiment, a transfer pattern including a predetermined fine pattern can be stably transferred to a transfer object.
< Film 30 for Pattern formation >)
The mask blank 10 for manufacturing a display device according to the present embodiment (hereinafter, may be simply referred to as "mask blank 10 of the present embodiment") has a front-side structure in a range where the incident energy of X-rays is 400eV or more and 402eV or less in the X-ray absorption spectrum of the thin film 30 obtained by the X-ray absorption spectroscopy.
The X-ray absorption spectrum can be obtained by a method of irradiating a sample (thin film) with X-rays, and measuring secondary electrons emitted from the sample to indirectly derive an X-ray absorption coefficient, a so-called electron yield method. The X-ray absorption spectrum may be obtained by a fluorescence yield method.
The inventors of the present invention have made the following presumption on the relationship between the trend of the X-ray absorption coefficient and the light resistance.
When the thin film 30 for forming a pattern containing a transition metal and silicon is formed on the light-transmitting substrate 20 by sputtering using a sputtering gas containing nitrogen in the film forming chamber, the nitrogen is considered to enter in a state of being bonded to the transition metal and silicon in the thin film 30. The inventors of the present invention obtained an X-ray absorption spectrum in the range of the incident X-ray energy derived from nitrogen by an X-ray absorption spectrum method, and as a result, found that: as shown in fig. 5 and 6, in the film 30 for patterning having good light resistance to exposure light, a pre-edge structure (pre-edge) which is a small peak of an X-ray Absorption coefficient appears in an incident X-ray Absorption energy (a range of 400eV to 402 eV) immediately before an incident X-ray Absorption energy (a range of 403eV to 406 eV) at which an Absorption edge (Absorption edge) which is a large peak of an X-ray Absorption coefficient appears. On the other hand, it was found that: in the film 30 having poor light resistance to exposure light, the front structure (pre-edge), which is the smaller peak of the X-ray Absorption coefficient, does not appear at the front incident X-ray Absorption energy (the range of 400eV to 402 eV) of the front incident X-ray Absorption energy (the range of 403eV to 406 eV) at which the Absorption edge (Absorption edge) is the larger peak of the X-ray Absorption coefficient appears.
In the thin film having a significant peak of the structure before the edge of nitrogen, nitrogen is considered to exist in a large amount in a state of being firmly bonded to other elements (mainly transition metal and silicon). To change the bonding state (strip electrons), more energy is required. Therefore, the deterioration of film quality (mainly, the combination of transition metal, silicon and nitrogen is released, and the transmittance increases due to the combination with oxygen) caused by the irradiation of ultraviolet energy of several eV requires more energy. As a result, it is presumed that: the film having a significant peak in the front structure is a film having high light resistance to exposure light having a wavelength including the ultraviolet region. But this speculation is based on current phase insights and does not limit the scope of the present invention in any way.
The X-ray absorption spectrum of the film 30 for patterning (hereinafter, sometimes simply referred to as "film 30") preferably has an absorption edge in a range of from 403eV to 406eV of incident X-ray energy. This is because a thin film having a absorption edge in this range of incident X-ray energy contains nitrogen at a certain ratio or more.
In the X-ray absorption spectrum of the thin film 30 for patterning, from the viewpoint of obtaining high light resistance to exposure light including wavelengths in the ultraviolet region, when the maximum value of the X-ray absorption coefficient at the absorption edge of the X-ray absorption spectrum of the thin film 30 is IA and the maximum value of the X-ray absorption spectrum at the structure before the edge is IP, the IA/IP preferably satisfies the relationship of 1.45 or less, and more preferably satisfies the relationship of 1.40 or less. On the other hand, the IA/IP is preferably 1.0 or more, more preferably 1.05 or more.
The X-ray absorption coefficient IA at the absorption edge is preferably the maximum value of the X-ray absorption coefficient when the incident X-ray energy is in the range of from 403eV to 406eV, and more preferably the maximum value of the X-ray absorption coefficient when the incident X-ray energy is in the range of from 404eV to 405 eV. The X-ray absorption coefficient IP at the structure in front of the edge is preferably the maximum value of the X-ray absorption coefficient when the incident X-ray energy is in the range of 400eV to 401 eV.
In the X-ray absorption spectrum of the thin film 30 for pattern formation, from the viewpoint of obtaining high light resistance to exposure light including wavelengths in the ultraviolet region, when the maximum value of the X-ray absorption coefficient at the structure before the edge is IP and the minimum value of the X-ray absorption coefficient at the valley of the X-ray absorption spectrum between the structure before the edge and the absorption edge is IV, the relationship of IP/IV of 1.0 or more is preferably satisfied. The X-ray absorption coefficient IV at the valley of the X-ray absorption spectrum between the pre-edge structure and the absorption edge is preferably the minimum of the X-ray absorption coefficients when the incident X-ray energy is in the range of more than 401eV and 402eV or less.
The thin film 30 for patterning may be made of a material containing a transition metal and silicon (Si). The transition metal is preferably molybdenum (Mo), tantalum (Ta), tungsten (W), titanium (Ti), zirconium (Zr), or the like, and more preferably titanium or molybdenum. In addition, the thin film 30 for patterning particularly preferably contains at least titanium as a transition metal.
The thin film 30 for pattern formation may be a phase shift film having a phase shift function.
The ratio of the content of the transition metal to the total content of the transition metal and silicon in the thin film 30 for pattern formation is preferably 0.05 or more, more preferably 0.10 or more. By satisfying these ratios, both optical characteristics and drug resistance can be made excellent. The ratio of the content of the transition metal to the total content of the transition metal and silicon in the thin film 30 for forming a pattern is preferably 0.50 or less, more preferably 0.40 or less. By satisfying these ratios, excessive increase in wet etching rate at the time of patterning of the thin film 30 for patterning can be suppressed.
The thin film 30 for patterning preferably contains nitrogen. In the above transition metal silicide, nitrogen as a light element component has an effect of not lowering the refractive index as compared with oxygen as a light element component. Therefore, by containing nitrogen in the thin film 30 for patterning, the film thickness for obtaining a desired phase difference (also referred to as a phase shift amount) can be made thin. The nitrogen content in the thin film 30 for patterning is preferably 10 atomic% or more, and more preferably 20 atomic% or more. On the other hand, the nitrogen content is preferably 60 at% or less, more preferably 55 at% or less. By increasing the nitrogen content in the thin film 30, the transmittance to exposure light can be suppressed from becoming too high.
In addition to the above oxygen and nitrogen, the thin film 30 for patterning may contain other light element components such as carbon and helium for the purpose of reducing film stress and controlling wet etching rate.
The thin film 30 for patterning may be composed of a plurality of layers or may be composed of a single layer. The film 30 for patterning composed of a single layer is preferable in that it is difficult to form an interface in the film 30 for patterning and the cross-sectional shape is easy to control. On the other hand, the thin film 30 for patterning composed of a plurality of layers is preferable in terms of ease of film formation and the like.
In order to secure optical performance, the film thickness of the thin film 30 for pattern formation is preferably 200nm or less, more preferably 180nm or less, and still more preferably 150nm or less. In order to ensure the desired transmittance, the film thickness of the thin film 30 for pattern formation is preferably 50nm or more, more preferably 60nm or more.
Transmittance and phase difference of film 30 for pattern formation
In the mask blank 10 for manufacturing a display device according to the present embodiment, the thin film 30 for forming a pattern is preferably a phase shift film having the following optical characteristics: the transmittance is 1% to 80% and the phase difference is 140 degrees to 210 degrees with respect to the representative wavelength of exposure light (light having a wavelength of 405 nm: h line). Unless otherwise specified, the transmittance in the present specification refers to a value obtained by conversion based on the transmittance of the light-transmitting substrate (100%).
When the thin film 30 for pattern formation is a phase shift film, the thin film 30 for pattern formation has a function of adjusting the reflectance (hereinafter, may be referred to as a back surface reflectance) of light incident from the light transmissive substrate 20 side and a function of adjusting the transmittance and the phase difference of exposure light.
The transmittance of the thin film 30 for pattern formation to exposure light satisfies a value required as the thin film 30 for pattern formation. The transmittance of the thin film 30 for pattern formation is preferably 1% or more and 80% or less, more preferably 3% or more and 65% or less, and still more preferably 5% or more and 60% or less, with respect to light of a predetermined wavelength (hereinafter referred to as a representative wavelength) included in the exposure light. That is, when the exposure light is a composite light including light in a wavelength range of 313nm to 436nm, the thin film 30 for pattern formation has the above-described transmittance for light of a representative wavelength included in the wavelength range. For example, when the exposure light is a composite light including i-line, h-line, and g-line, the film 30 for patterning can have the above-described transmittance for any of the i-line, h-line, and g-line. The representative wavelength may be, for example, an h-line having a wavelength of 405 nm. By having such characteristics for the h-line, even when the composite light including the i-line, the h-line, and the g-line is used as the exposure light, similar effects can be expected for the transmittance at the wavelengths of the i-line and the g-line.
When the exposure light is selected monochromatic light obtained by blocking a certain wavelength range from 313nm to 436nm by a filter or the like, and monochromatic light selected from a wavelength range from 313nm to 436nm, the thin film 30 for pattern formation has the above-described transmittance for the monochromatic light of the single wavelength.
The transmittance can be measured using a phase shift measuring device or the like.
The phase difference of the pattern forming film 30 with respect to the exposure light satisfies a value required as the pattern forming film 30. The phase difference of the thin film 30 for pattern formation is preferably 140 degrees or more and 210 degrees or less, more preferably 160 degrees or more and 200 degrees or less, and still more preferably 170 degrees or more and 190 degrees or less, with respect to the light of the representative wavelength included in the exposure light. By virtue of this property, the phase of the light of the representative wavelength contained in the exposure light can be changed to 140 degrees or more and 210 degrees or less. Therefore, a phase difference of 140 degrees or more and 210 degrees or less is generated between the light of the representative wavelength transmitted through the thin film 30 for pattern formation and the light of the representative wavelength transmitted through only the light-transmitting substrate 20. That is, when the exposure light is a composite light including light in a wavelength range of 313nm to 436nm, the thin film 30 for pattern formation has the above-described phase difference with respect to light of a representative wavelength included in the wavelength range. For example, when the exposure light is a composite light including i-line, h-line, and g-line, the film 30 for forming a pattern can have the above-described phase difference with respect to any one of the i-line, h-line, and g-line. The representative wavelength may be, for example, an h-line having a wavelength of 405 nm. By having such characteristics for the h-line, in the case of using the composite light including the i-line, the h-line, and the g-line as the exposure light, similar effects can be expected also for the phase difference at the wavelengths of the i-line and the g-line.
The phase difference can be measured using a phase shift amount measuring device or the like.
The back surface reflectance of the film 30 for pattern formation is 15% or less, preferably 10% or less in a wavelength region of 365nm to 436 nm. When the exposure light includes the j line (wavelength 313 nm), the back surface reflectance of the thin film 30 for pattern formation is preferably 20% or less, more preferably 17% or less, with respect to light in the wavelength range from 313nm to 436 nm. More preferably 15% or less. The back surface reflectance of the film 30 for pattern formation is 0.2% or more in the wavelength region of 365nm to 436nm, preferably 0.2% or more for light in the wavelength region of 313nm to 436 nm.
The back surface reflectance can be measured using a spectrophotometer or the like.
The thin film 30 for patterning can be formed by a known film forming method such as sputtering.
Etching mask film 40 >
The mask plate 10 for manufacturing a display device according to the present embodiment preferably includes an etching mask film 40 having a different etching selectivity with respect to the thin film 30 for forming a pattern on the thin film 30 for forming a pattern.
The etching mask film 40 is disposed above the thin film 30 for pattern formation, and is made of a material having etching resistance (etching selectivity different from that of the thin film 30 for pattern formation) to an etching solution for etching the thin film 30 for pattern formation. In addition, the etching mask film 40 may have a function of blocking transmission of exposure light. The etching mask film 40 may have a function of reducing the film surface reflectance so that the film surface reflectance of the thin film 30 for pattern formation is 15% or less in a wavelength region of 350nm to 436nm with respect to light incident from the thin film 30 for pattern formation.
The etching mask film 40 is preferably made of a chromium-based material containing chromium (Cr). The etching mask film 40 is more preferably made of a material containing chromium and substantially no silicon. Substantially free of silicon means that the silicon content is less than 2% (except for the composition inclined region of the interface of the thin film 30 for pattern formation and the etching mask film 40). More specifically, the chromium-based material may be a material containing chromium (Cr), or at least one of chromium (Cr), oxygen (O), nitrogen (N), and carbon (C). The chromium-based material may contain chromium (Cr), at least one of oxygen (O), nitrogen (N), and carbon (C), and further contains fluorine (F). For example, cr, crO, crN, crF, crCO, crCN, crON, crCON and CrCONF are examples of the material constituting the etching mask film 40.
The etching mask film 40 can be formed by a known film forming method such as a sputtering method.
In the case where the etching mask film 40 has a function of blocking the transmission of exposure light, the optical concentration of exposure light is preferably 3 or more, more preferably 3.5 or more, and even more preferably 4 or more in the portion where the thin film 30 for pattern formation and the etching mask film 40 are stacked. The optical density can be measured using a spectrophotometer, an OD meter (densitometer), or the like.
The etching mask film 40 can be made into a single film having a uniform composition according to functions. In addition, the etching mask film 40 may be a plurality of films having different compositions. In addition, the etching mask film 40 may be a single film whose composition continuously varies in the thickness direction.
The mask blank 10 of the present embodiment shown in fig. 1 includes an etching mask film 40 on the thin film 30 for pattern formation. The mask 10 of the present embodiment includes a mask 10 having a structure in which an etching mask film 40 is provided on a thin film 30 for pattern formation, and a resist film is provided on the etching mask film 40.
Method for producing mask plate 10
Next, a method for manufacturing the mask blank 10 according to the embodiment shown in fig. 1 will be described. The mask blank 10 shown in fig. 1 is manufactured by performing the following thin film forming step for pattern formation and etching mask film forming step. The mask blank 10 shown in fig. 2 is manufactured by a thin film forming process for pattern formation.
The steps are described in detail below.
Thin film forming process for pattern formation
First, the light-transmissive substrate 20 is prepared. The light-transmitting substrate 20 may be made of a glass material selected from synthetic quartz glass, aluminosilicate glass, soda lime glass, low thermal expansion glass (SiO 2-TiO2 glass, etc.), and the like, as long as it is transparent to exposure light.
Next, a thin film 30 for pattern formation is formed on the light-transmitting substrate 20 by sputtering.
The film 30 for patterning can be formed under a predetermined sputtering gas atmosphere using a predetermined sputtering target. The predetermined sputtering target is, for example, a transition metal silicide target containing a transition metal and silicon as main components of a material constituting the thin film 30 for pattern formation, or a transition metal silicide nitride target containing a transition metal, silicon and nitrogen. The predetermined sputtering gas atmosphere is, for example, a sputtering gas atmosphere composed of an inert gas including argon or a sputtering gas atmosphere composed of a mixed gas including the inert gas, nitrogen, and a gas selected from the group consisting of oxygen, carbon dioxide, nitrogen monoxide, and nitrogen dioxide, as the case may be. The formation of the thin film 30 for pattern formation may be performed in the following state: the gas pressure in the film forming chamber during sputtering is 0.3Pa or more and 2.0Pa or less, preferably 0.43Pa or more and 0.9Pa or less. Side etching at the time of pattern formation can be suppressed, and a high etching rate can be achieved. The atomic ratio of the transition metal to silicon of the transition metal silicide target is preferably in the range of transition metal to silicon=1:1 to 1:19 from the viewpoint of improving light resistance, the viewpoint of adjusting transmittance, and the like.
The composition and thickness of the film 30 for patterning are adjusted so that the film 30 for patterning has the above-described phase difference and transmittance. The composition of the thin film 30 for patterning can be controlled by the content ratio of elements constituting the sputtering target (for example, the ratio of the content of transition metal to the content of silicon), the composition and flow rate of the sputtering gas, and the like. The thickness of the thin film 30 for pattern formation can be controlled by sputtering power, sputtering time, and the like. The thin film 30 for patterning is preferably formed using an in-line sputtering apparatus. In the case where the sputtering apparatus is an in-line sputtering apparatus, the thickness of the thin film 30 for pattern formation can be controlled by the conveyance speed of the substrate. In this way, in the thin film 30 for patterning, the X-ray absorption spectrum is controlled so as to satisfy a desired relationship (a range of 400eV to 402eV inclusive has a front-side structure, etc.).
These film forming conditions are conditions inherent to the film forming apparatus, and are appropriately adjusted so that the formed film has desired optical characteristics.
When the thin film 30 for patterning is composed of a single film, the composition and flow rate of the sputtering gas are appropriately adjusted, and the film formation process described above is performed only 1 time. When the thin film 30 for patterning is composed of a plurality of films having different compositions, the above-described film formation process is performed a plurality of times by appropriately adjusting the composition and flow rate of the sputtering gas. Targets having different content ratios of elements constituting the sputtering target may be used to form the thin film 30 for patterning. In the case of performing the film forming process a plurality of times, the sputtering power applied to the sputtering target may be changed for each film forming process.
Thus, the mask blank 10 of the present embodiment can be obtained.
Etching mask film forming process
The mask plate 10 of the present embodiment may further have an etching mask film 40. The following etching mask film formation step was further performed. In addition, the etching mask film 40 is preferably composed of a material containing chromium.
After the thin film forming step for pattern formation, surface treatment is performed to adjust the state of surface oxidation of the surface of the thin film 30 for pattern formation as needed, and then an etching mask film 40 is formed on the thin film 30 for pattern formation by a sputtering method. The etching mask film 40 is preferably formed using an in-line sputtering apparatus. In the case where the sputtering apparatus is an in-line sputtering apparatus, the thickness of the etching mask film 40 can be controlled by the conveyance speed of the transparent substrate 20.
The etching mask film 40 can be formed in a sputtering gas atmosphere composed of an inert gas or a sputtering gas atmosphere composed of a mixed gas of an inert gas and an active gas, using a sputtering target containing chromium or a chromium compound (chromium oxide, chromium nitride, chromium carbide, chromium oxide nitride, chromium nitride carbide, chromium oxide nitride carbide, or the like). The inert gas may contain, for example, at least one selected from the group consisting of helium, neon, argon, krypton, and xenon. The reactive gas may contain at least one selected from the group consisting of oxygen gas, nitrogen gas, nitric oxide gas, nitrogen dioxide gas, carbon dioxide gas, hydrocarbon-based gas, and fluorine-based gas. Examples of the hydrocarbon gas include methane gas, butane gas, propane gas, and styrene gas. By adjusting the gas pressure in the film forming chamber during sputtering, the etching mask film 40 can have a columnar structure as in the thin film 30 for pattern formation. This suppresses side etching at the time of pattern formation, which will be described later, and achieves a high etching rate.
In the case where the etching mask film 40 is composed of a single film having a uniform composition, the above-described film formation process is performed only 1 time without changing the composition and flow rate of the sputtering gas. In the case where the etching mask film 40 is composed of a plurality of films having different compositions, the above-described film forming process is performed a plurality of times by changing the composition and flow rate of the sputtering gas in each film forming process. When the etching mask film 40 is composed of a single film whose composition continuously changes in the thickness direction, the film formation process is performed only 1 time while changing the composition and flow rate of the sputtering gas with the passage of time of the film formation process.
In this way, the mask plate 10 of the present embodiment having the etching mask film 40 can be obtained.
Further, since the mask blank 10 shown in fig. 1 includes the etching mask film 40 on the thin film 30 for pattern formation, the etching mask film forming process is performed at the time of manufacturing the mask blank 10. In the case of manufacturing the mask 10 including the etching mask film 40 on the thin film 30 for pattern formation and the resist film on the etching mask film 40, the resist film is formed on the etching mask film 40 after the etching mask film forming step. In the mask blank 10 shown in fig. 2, when the mask blank 10 having a resist film on the thin film 30 for pattern formation is manufactured, the resist film is formed after the thin film forming process for pattern formation.
The mask blank 10 of the embodiment shown in fig. 1 has an etching mask film 40 formed on a thin film 30 for pattern formation. In addition, the mask 10 of the embodiment shown in fig. 2 is formed with a thin film 30 for pattern formation. In any case, the X-ray absorption spectrum of the film 30 for patterning satisfies a desired relationship (a range of 400eV to 402eV inclusive has a front-edge structure or the like).
The mask blank 10 of the embodiment shown in fig. 1 and 2 has high light resistance to exposure light having a wavelength including an ultraviolet region. Therefore, even after the exposure light having a wavelength including the ultraviolet region is irradiated, the thin film pattern 30a for forming a pattern, which can maintain the exposure transfer characteristic within a desired range, can be formed.
Therefore, by using the mask blank 10 of the present embodiment, the transfer mask 100 having high light resistance to exposure light having a wavelength including the ultraviolet region and capable of transferring the thin film pattern 30a for forming a high-definition pattern with high accuracy can be manufactured.
Method for manufacturing transfer mask 100
Next, a method for manufacturing the transfer mask 100 according to the present embodiment will be described. The transfer mask 100 has the same technical features as the mask blank 10. The matters of the transparent substrate 20, the thin film 30 for pattern formation, and the etching mask film 40 in the transfer mask 100 are the same as those of the mask blank 10.
Fig. 3 is a schematic diagram showing a method for manufacturing the transfer mask 100 according to the present embodiment. Fig. 4 is a schematic diagram showing another method for manufacturing the transfer mask 100 according to the present embodiment.
Method for manufacturing transfer mask 100 shown in FIG. 3
The method for manufacturing the transfer mask 100 shown in fig. 3 is a method for manufacturing the transfer mask 100 using the mask blank 10 shown in fig. 1. The method for manufacturing the transfer mask 100 shown in fig. 3 includes: a step of preparing the mask plate shown in fig. 1; a step of forming a resist film having a transfer pattern on the etching mask film 40; performing wet etching using the resist film as a mask to form a transfer pattern on the etching mask film 40; and performing wet etching using the etching mask film (first etching mask film pattern 40 a) on which the transfer pattern is formed as a mask, to form a transfer pattern on the thin film 30 for pattern formation. In addition, the transfer pattern in the present specification is obtained by patterning at least 1 optical film formed on the light transmissive substrate 20. The optical film may be the thin film 30 for patterning and/or the etching mask film 40, or may further include other films (light-shielding film, film for suppressing reflection, conductive film, etc.). That is, the transfer pattern may include a thin film for patterning and/or an etching mask film obtained by patterning, or may further include another film obtained by patterning.
In the method for manufacturing the transfer mask 100 shown in fig. 3, specifically, a resist film is formed on the etching mask film 40 of the mask blank 10 shown in fig. 1. Next, a desired pattern is drawn and developed on the resist film to form a resist film pattern 50 (see fig. 3 (a), a step of forming the first resist film pattern 50). Next, the etching mask film 40 is wet etched using the resist film pattern 50 as a mask, and an etching mask film pattern 40a is formed on the thin film 30 for pattern formation (see fig. 3 (b), a step of forming the first etching mask film pattern 40 a). Next, the thin film for pattern formation 30 is wet etched using the etching mask film pattern 40a as a mask, and a thin film pattern for pattern formation 30a is formed on the light-transmissive substrate 20 (see fig. 3 (c), a process of forming the thin film pattern for pattern formation 30 a). Then, the formation process of the second resist film pattern 60 and the formation process of the second etching mask film pattern 40b may be further included (refer to (d) and (e) of fig. 3).
More specifically, in the step of forming the first resist film pattern 50, first, a resist film is formed on the etching mask film 40 of the mask plate 10 of the present embodiment shown in fig. 1. The resist film material used is not particularly limited. The resist film may be formed by, for example, exposing a laser beam having any wavelength selected from a wavelength region of 350nm to 436nm, which will be described later. The resist film may be either positive or negative.
Then, a desired pattern is drawn on the resist film using a laser having any one wavelength selected from the wavelength region of 350nm to 436 nm. The pattern drawn on the resist film is a pattern formed on the thin film 30 for pattern formation. Examples of the pattern drawn on the resist film include a line and space pattern and a hole pattern.
Then, the resist film is developed with a predetermined developer, and as shown in fig. 3 (a), a first resist film pattern 50 is formed on the etching mask film 40.
Formation process of first etching mask film pattern 40a
In the first etching mask film pattern 40a forming step, first, the etching mask film 40 is etched using the first resist film pattern 50 as a mask, thereby forming the first etching mask film pattern 40a. The etching mask film 40 may be formed of a chromium-based material containing chromium (Cr).
Thereafter, the first resist film pattern 50 is stripped as shown in fig. 3 (b) using a resist stripping liquid or by ashing. In some cases, the subsequent step of forming the thin film pattern 30a for pattern formation may be performed without peeling the first resist film pattern 50.
Process for forming thin film pattern 30a for pattern formation
In the step of forming the first pattern-forming thin film pattern 30a, the pattern-forming thin film 30 is wet etched using the first etching mask film pattern 40a as a mask, and as shown in fig. 3 (c), the pattern-forming thin film pattern 30a is formed. The thin film pattern 30a for pattern formation includes a line and space pattern and a hole pattern. The etching liquid for etching the thin film 30 for pattern formation is not particularly limited as long as the thin film 30 for pattern formation can be selectively etched. Examples thereof include an etching solution containing ammonium bifluoride and hydrogen peroxide, and an etching solution containing ammonium bifluoride, phosphoric acid and hydrogen peroxide.
In order to make the cross-sectional shape of the pattern-forming thin film pattern 30a good, the wet etching is preferably performed for a time (overetching time) longer than a time (etching time) until the light-transmissive substrate 20 is exposed in the pattern-forming thin film pattern 30 a. In consideration of the influence on the transparent substrate 20, the overetch time is preferably a time obtained by adding 20% of the overetch time to the overetch time, and more preferably a time obtained by adding 10% of the overetch time to the overetch time.
Formation process of second resist film pattern 60
In the second resist film pattern 60 forming step, first, a resist film is formed to cover the first etching mask film pattern 40 a. The resist film material used is not particularly limited. For example, the laser light having any wavelength selected from the wavelength range of 350nm to 436nm described later may be subjected to photosensing. The resist film may be either positive or negative.
Then, a desired pattern is drawn on the resist film using a laser having any one wavelength selected from the wavelength region of 350nm to 436 nm. The pattern drawn on the resist film is a light shielding band pattern for shielding the outer peripheral region of the region where the pattern forming thin film pattern 30a is formed, a light shielding band pattern for shielding the central portion of the pattern forming thin film pattern 30a, and the like. In addition, depending on the transmittance of the pattern forming thin film 30 to exposure light, the pattern drawn on the resist film may be a pattern with a light shielding band which does not shield the central portion of the pattern forming thin film pattern 30 a.
Then, the resist film is developed with a predetermined developer, and as shown in fig. 3 (d), a second resist film pattern 60 is formed on the first etching mask film pattern 40 a.
Formation process of second etching mask film pattern 40b
In the step of forming the second etching mask film pattern 40b, the first etching mask film pattern 40a is etched using the second resist film pattern 60 as a mask, and as shown in fig. 3 (e), the second etching mask film pattern 40b is formed. The first etching mask film pattern 40a may be formed of a chromium-based material containing chromium (Cr). The etching liquid for etching the first etching mask film pattern 40a is not particularly limited as long as it can selectively etch the first etching mask film pattern 40 a. For example, an etching solution containing ceric ammonium nitrate and perchloric acid is given.
Then, the second resist film pattern 60 is stripped using a resist stripping liquid or by ashing.
In this way, the transfer mask 100 can be obtained. That is, the transfer pattern included in the transfer mask 100 of the present embodiment may include the thin film pattern 30a for pattern formation and the second etching mask film pattern 40b.
In the above description, the etching mask film 40 has been described as having a function of blocking the transmission of exposure light. In the above description, the second resist film pattern 60 and the second etching mask film pattern 40b are not formed in the case where the etching mask film 40 has only the function of a hard mask for etching the thin film 30 for forming a pattern. In this case, after the step of forming the thin film pattern 30a for pattern formation, the first etching mask film pattern 40a is peeled off, and the transfer mask 100 is produced. That is, the transfer pattern included in the transfer mask 100 may be constituted only by the thin film pattern 30a for pattern formation.
According to the method for manufacturing the transfer mask 100 of the present embodiment, since the mask plate 10 shown in fig. 1 is used, the transfer mask 100 having high light resistance to exposure light having a wavelength including an ultraviolet region and capable of transferring the high-definition pattern-forming thin film pattern 30a with high accuracy can be manufactured. The transfer mask 100 thus manufactured can cope with miniaturization of the line and space pattern and/or the contact hole. In addition, since the transfer mask has particularly high light resistance, a long service life as a transfer mask can be realized.
Method for manufacturing transfer mask 100 shown in FIG. 4
The method for manufacturing the transfer mask 100 shown in fig. 4 is a method for manufacturing the transfer mask 100 using the mask blank 10 shown in fig. 2. The method for manufacturing the transfer mask 100 shown in fig. 4 includes: a step of preparing the mask plate 10 shown in fig. 2; and forming a resist film on the thin film 30 for pattern formation, and wet etching the thin film 30 for pattern formation using the resist film pattern formed of the resist film as a mask to form a transfer pattern on the light-transmissive substrate 20.
Specifically, in the method for manufacturing the transfer mask 100 shown in fig. 4, a resist film is formed on the mask plate 10. Next, a desired pattern is drawn and developed on the resist film, thereby forming a resist film pattern 50 (fig. 4 (a), a first resist film pattern 50 forming step). Next, the thin film for pattern formation 30 is wet etched using the resist film pattern 50 as a mask, and a thin film pattern for pattern formation 30a is formed on the light-transmissive substrate 20 (fig. 4 (b) and (c), and a process for forming the thin film pattern for pattern formation 30 a).
More specifically, in the resist film pattern forming step, first, a resist film is formed on the thin film 30 for pattern formation of the mask blank 10 of the present embodiment shown in fig. 2. The resist film material used is the same as that described above. Before the resist film is formed as needed, the film 30 for patterning may be subjected to a surface modification treatment in order to improve adhesion between the film 30 for patterning and the resist film. In the same manner as described above, after forming the resist film, a desired pattern is drawn on the resist film using a laser having any one wavelength selected from the wavelength range of 350nm to 436 nm. Then, the resist film is developed with a predetermined developer, and as shown in fig. 4 (a), a resist film pattern 50 is formed on the thin film 30 for pattern formation.
Process for forming thin film pattern 30a for pattern formation
In the step of forming the thin film pattern 30a for pattern formation, the thin film 30 for pattern formation is etched using the resist film pattern as a mask, and as shown in fig. 4 (b), the thin film pattern 30a for pattern formation is formed. The etching solution and the overetching time for etching the pattern forming thin film pattern 30a and the pattern forming thin film 30 are the same as those described in the embodiment shown in fig. 3.
After that, the resist film pattern 50 is peeled off using a resist peeling liquid or by ashing (fig. 4 (c)).
In this way, the transfer mask 100 can be obtained. The transfer pattern included in the transfer mask 100 of the present embodiment is constituted only by the thin film pattern 30a for pattern formation, but may also include other film patterns. Examples of the other film include a film for suppressing reflection and a conductive film.
According to the method for manufacturing the transfer mask 100 of this embodiment, since the mask plate 10 shown in fig. 2 is used, the transfer mask 100 having high light resistance to exposure light including the wavelength of the ultraviolet region and capable of transferring the high-definition pattern-forming thin film pattern 30a with high accuracy can be manufactured. The transfer mask 100 thus manufactured can cope with miniaturization of the line and space pattern and/or the contact hole.
Method for manufacturing display device
A method for manufacturing a display device according to this embodiment will be described. The method for manufacturing a display device according to the present embodiment includes an exposure step of placing the transfer mask 100 for manufacturing a display device according to the present embodiment described above on a mask stage of an exposure device, and exposing and transferring a transfer pattern formed on the transfer mask 100 to a resist film formed on a substrate for a display device.
Specifically, the method for manufacturing a display device according to the present embodiment includes: a step of placing the transfer mask 100 manufactured using the mask blank 10 on a mask stage of an exposure apparatus (mask placing step); and a step (exposure step) of transferring the transfer pattern to a resist film on a substrate for a display device. The steps are described in detail below.
Mounting step
In the mounting step, the transfer mask 100 according to the present embodiment is mounted on a mask stage of an exposure apparatus. Here, the transfer mask 100 is disposed so as to face a resist film formed on a substrate for a display device through a projection optical system of an exposure apparatus.
Pattern transfer process
In the pattern transfer step, exposure light is irradiated to the transfer mask 100, and a transfer pattern including the thin film pattern 30a for pattern formation is transferred onto a resist film formed on a substrate for a display device. The exposure light is a composite light including light having a plurality of wavelengths selected from the wavelength range of 313nm to 436nm, or monochromatic light selected by cutting off a certain wavelength range from the wavelength range of 313nm to 436nm through a filter or the like, or monochromatic light emitted from a light source having a wavelength range of 313nm to 436 nm. For example, the exposure light is a composite light including at least one of an i line, an h line, and a g line, or a monochromatic light of the i line. By using the composite light as the exposure light, the exposure light intensity can be increased to improve productivity. Therefore, the manufacturing cost of the display device can be reduced.
According to the method for manufacturing a display device of the present embodiment, a high-definition display device having a fine line and space pattern and/or a contact hole can be manufactured with high resolution.
In the above embodiment, the case of using the mask blank 10 having the thin film 30 for pattern formation and the transfer mask 100 having the thin film pattern 30a for pattern formation has been described. The thin film 30 for pattern formation may be, for example, a phase shift film or a light shielding film having a phase shift effect. Therefore, the transfer mask 100 of the present embodiment includes a phase shift mask having a phase shift film pattern and a binary mask having a light shielding film pattern. The mask blank 10 of the present embodiment includes a phase shift mask blank and a binary mask blank, which are raw materials of the phase shift mask and the binary mask.
Examples (example)
Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.
Example 1
To manufacture the mask blank 10 of example 1, first, a synthetic quartz glass substrate having 1214 dimensions (1220 mm×1400 mm) was prepared as the light-transmitting substrate 20.
Then, the synthetic quartz glass substrate is mounted on a tray (not shown) with its main surface facing downward, and is carried into a chamber of an in-line sputtering apparatus.
In order to form the thin film 30 for patterning on the main surface of the light-transmissive substrate 20, first, a mixed gas composed of argon (Ar) gas and nitrogen (N 2) gas is introduced into the first chamber. In example 1, the flow ratio (N 2/Ar) of nitrogen (N 2) to argon (Ar) was 1.107. Then, using a first sputtering target containing titanium and silicon, a nitride of titanium silicide containing titanium, silicon, and nitrogen is deposited on the main surface of the light-transmitting substrate 20 by reactive sputtering. The sputtering voltage at this time was 480[ V ]. Thus, a thin film 30 for pattern formation having a film thickness of 113nm and made of titanium silicide nitride (Ti: si: N: O=10.7:34.9:50.3:4.1 atomic%) was formed. Here, the composition of the thin film 30 for patterning was obtained by measuring a thin film formed under the same film forming conditions as in example 1 by X-ray photoelectron spectroscopy (XPS). Hereinafter, the same applies to other films (the same applies to examples 2, 3, 1 and 2 below). The ratio of the titanium content to the total content of titanium and silicon in the thin film 30 for forming a pattern is 0.235 or more and 0.05 or more.
The thin film 30 for pattern formation is a phase shift film having a phase shift effect.
Next, the light-transmissive substrate 20 with the thin film 30 for pattern formation is carried into the second chamber, and a mixed gas of argon (Ar) gas and nitrogen (N 2) gas is introduced into the second chamber. Then, a second sputtering target made of chromium is used, and a chromium nitride (CrN) containing chromium and nitrogen is formed on the thin film 30 for pattern formation by reactive sputtering. Next, a mixed gas of argon (Ar) gas and methane (CH 4) gas was introduced while keeping the third chamber at a predetermined vacuum degree, and a chromium carbide (CrC) containing chromium and carbon was formed on CrN by reactive sputtering using a third sputtering target composed of chromium. Finally, a mixed gas of argon (Ar) gas and methane (CH 4) gas, and a mixed gas of nitrogen (N 2) gas and oxygen (O 2) gas were introduced into the fourth chamber in a state where the fourth chamber was set to a predetermined vacuum degree, and a fourth sputtering target made of chromium was used to form chromium carbonitride (Cr CON) containing chromium, carbon, oxygen and nitrogen on CrC by reactive sputtering. As described above, the etching mask film 40 having a laminated structure of the CrN layer, the CrC layer, and the CrCON layer is formed on the thin film 30 for patterning.
Thus, the mask blank 10 in which the thin film 30 for pattern formation and the etching mask film 40 were formed on the light-transmissive substrate 20 was obtained.
The thin film for pattern formation of example 1 was formed on the main surface of another synthetic quartz substrate (about 152 mm. Times.152 mm), and the other thin film for pattern formation was formed under the same film formation conditions as in example 1. Next, an X-ray absorption microstructure analysis was performed on a sample obtained by cutting a thin film for patterning on the other synthetic quartz substrate into a predetermined size by an X-ray absorption spectrometry (electron yield method), and an X-ray absorption spectrum was obtained. Specifically, the processing was performed at the known synchrotron optical center (Aichi Synchrotron Radiation Center) BL7U (the same applies to examples 2 and 3 and comparative examples 1 and 2).
Fig. 5 is a graph showing an X-ray absorption spectrum (horizontal axis: X-ray energy incident on the film, vertical axis: X-ray absorption coefficient to the X-ray energy) obtained by an X-ray absorption spectrometry for the films for patterning of the mask plates of examples 1 to 3 and comparative examples 1 and 2 of the present invention. Fig. 6 is an enlarged view showing a main part of an X-ray absorption spectrum (horizontal axis: X-ray energy incident on the film, vertical axis: X-ray absorption coefficient to the X-ray energy) obtained by an X-ray absorption spectrum method for the films for pattern formation of the mask plates of examples 1 to 3 and comparative examples 1 and 2 of the present invention.
As shown in fig. 5 and 6, the X-ray absorption spectrum of example 1 has a front-side structure in a range of 400eV to 402eV, and has an absorption side in a range of 403eV to 406 eV. As is found from the values shown in fig. 5, when the maximum value of the X-ray absorption coefficient at the absorption edge of the X-ray absorption spectrum of the thin film 30 (the maximum value of the X-ray absorption coefficient when the incident X-ray energy is 404.8eV in this example 1) is IA, and the maximum value of the X-ray absorption spectrum at the structure before the edge (the maximum value of the X-ray absorption coefficient when the incident X-ray energy is 400eV to 401eV in this example 1, the X-ray absorption coefficient when the incident X-ray energy is 400.8eV in this example 1) is IP, the IA/IP in example 1 is 1.153, and the relationship of 1.45 or less is satisfied.
Determination of transmittance and phase Difference
The transmittance (wavelength: 405 nm) and the phase difference (wavelength: 405 nm) of the surface of the thin film 30 for patterning of the mask blank 10 of example 1 were measured. In the measurement of the transmittance and the retardation of the film for pattern formation 30, a substrate with a film in which another film for pattern formation was formed on the main surface of the above-described another synthetic quartz glass substrate was used (the same applies to examples 2 and 3 and comparative examples 1 and 2). As a result, the transmittance of the other film for pattern formation (film for pattern formation 30) in example 1 was 35.2%, and the phase difference was 140 degrees.
Mask 100 for transfer and method for manufacturing the same
The transfer mask 100 was manufactured using the mask blank 10 of example 1 manufactured as described above. First, a photoresist film is coated on the etching mask film 40 of the mask plate 10 using a resist coating apparatus.
Then, a photoresist film is formed through a heating and cooling process.
Then, the photoresist film was drawn by using a laser drawing device, and a resist film pattern having a hole pattern with a hole diameter of 1.5 μm was formed on the etching mask film 40 by a developing and rinsing process.
Then, the etching mask film 40 is wet etched using a chromium etching solution containing ceric ammonium nitrate and perchloric acid with the resist film pattern as a mask, thereby forming a first etching mask film pattern 40a.
Then, the thin film for pattern formation 30 is wet etched using the titanium silicide etching solution obtained by diluting the mixture solution of ammonium bifluoride and hydrogen peroxide with pure water using the first etching mask film pattern 40a as a mask, thereby forming a thin film pattern for pattern formation 30a.
Then, the resist film pattern is peeled off.
Then, a photoresist film is coated so as to cover the first etching mask film pattern 40a using a resist coating apparatus.
Then, a photoresist film is formed through a heating and cooling process.
Then, the photoresist film is drawn by using a laser drawing device, and a second resist film pattern 60 for forming a light shielding tape is formed on the first etching mask film pattern 40a through a developing and rinsing process.
Then, the first etching mask film pattern 40a formed in the transfer pattern formation region is wet etched using a chromium etching solution containing ceric ammonium nitrate and perchloric acid with the second resist film pattern 60 as a mask.
Then, the second resist film pattern 60 is peeled off.
Thus, the transfer mask 100 of example 1 was obtained: on the light-transmitting substrate 20, a pattern-forming thin film pattern 30a having an aperture of 1.5 μm and a light shielding tape constituted by a laminated structure of the pattern-forming thin film pattern 30a and the etching mask film pattern 40b were formed in the transfer pattern formation region.
< Cross-sectional shape of transfer mask 100 >
The cross section of the transfer mask 100 thus obtained was observed by a scanning electron microscope.
The thin film pattern 30a for pattern formation of the transfer mask 100 of example 1 has a nearly vertical cross-sectional shape. Therefore, the thin film pattern 30a for pattern formation formed on the transfer mask 100 of example 1 has a cross-sectional shape that can sufficiently exhibit the phase shift effect.
From the above, it can be said that when the transfer mask 100 of example 1 is set on the mask stage of the exposure apparatus and the resist film transferred onto the substrate for the display apparatus is exposed, the transfer pattern including the fine pattern smaller than 2.0 μm can be transferred with high accuracy.
< Lightfastness >
A sample in which the thin film 30 for pattern formation used in the mask blank 10 of example 1 was formed on the light-transmissive substrate 20 was prepared. The film 30 for patterning of the sample of example 1 was irradiated with light of a metal halide light source including ultraviolet rays having a wavelength of 405nm so that the total irradiation amount was 10kJ/cm 2. The light resistance of the film 30 for pattern formation was evaluated by measuring the transmittance before and after the predetermined ultraviolet irradiation and calculating the change in the transmittance [ (transmittance after the ultraviolet irradiation) - (transmittance before the ultraviolet irradiation) ]. The transmittance was measured using a spectrophotometer.
Fig. 7 is a graph showing the relationship between IA/IP and transmittance changes in the thin films for patterning of the mask plates of examples 1 to 3 and comparative examples 1 and 2 of the present invention. As shown in fig. 7, in example 1, the change in transmittance before and after ultraviolet irradiation was good, and was 0.34%. From the above, the film for pattern formation of example 1 was a film having sufficiently high light resistance in practical use.
From the above, it is clear that the film for pattern formation of example 1 is an unprecedented excellent film satisfying the requirements of desired optical characteristics (transmittance, retardation) and high light resistance to exposure light including wavelengths in the ultraviolet region.
Example 2
The mask blank 10 of example 2 was manufactured in the same manner as the mask blank 10 of example 1, except that the thin film 30 for patterning was formed as described below.
The method for forming the thin film 30 for pattern formation of example 2 is as follows.
In order to form the thin film 30 for patterning on the main surface of the light-transmissive substrate 20, first, a mixed gas composed of argon (Ar) gas and nitrogen (N 2) gas is introduced into the first chamber. In example 2, the flow ratio (N 2/Ar) of nitrogen (N 2) to argon (Ar) was 1.107. Then, using a first sputtering target containing titanium and silicon, a nitride of titanium silicide containing titanium, silicon, and nitrogen is deposited on the main surface of the light-transmitting substrate 20 by reactive sputtering. Thus, a thin film 30 for pattern formation having a film thickness of 124nm and made of titanium silicide nitride (Ti: si: N: O=11.0:33.8:50.1:5.1 atomic%) was formed. The sputtering voltage at this time was 515[ V ]. The composition of the film 30 in example 2 is substantially the same as that of the film 30 in example 1. The ratio of the titanium content to the total content of titanium and silicon in the thin film 30 for forming a pattern is 0.05 or more.
Then, the etching mask film 40 was formed in the same manner as in example 1.
Then, another thin film for pattern formation was formed on the main surface of the other synthetic quartz substrate under the same film formation conditions as in example 2. Next, as for a sample obtained by cutting the thin film for patterning on the other synthetic quartz substrate into a predetermined size, an X-ray absorption microstructure analysis was performed by the X-ray absorption spectrometry (electron yield method) in the same manner as in example 1, and an X-ray absorption spectrum was obtained.
As shown in fig. 5 and 6, the X-ray absorption spectrum of example 2 has a front-side structure in a range of 400eV to 402eV, and has an absorption side in a range of 403eV to 406 eV. The shape of the X-ray absorption spectrum in example 2 is the same as that in example 1.
As is found from the values shown in fig. 5 and 6, IA/IP in example 2 is 1.128 (IA is an X-ray absorption coefficient when the incident X-ray energy is 405.1eV, IP is an X-ray absorption coefficient when the incident X-ray energy is 401.0eV in this example 2), and satisfies a relationship of 1.45 or less.
Determination of transmittance and phase Difference
The transmittance (wavelength: 405 nm) and the phase difference (wavelength: 405 nm) of the surface of the thin film 30 for patterning of the mask blank 10 of example 2 were measured. As a result, the film 30 for pattern formation in example 2 had a transmittance of 31.1% and a retardation of 147 degrees.
Mask 100 for transfer and method for manufacturing the same
Using the mask blank 10 of example 2 manufactured as described above, the transfer mask 100 was manufactured in the same manner as in example 1, and the transfer mask 100 of example 2 was obtained as described above: on the light-transmitting substrate 20, a pattern-forming thin film pattern 30a having an aperture of 1.5 μm and a light-shielding tape having a laminated structure of the pattern-forming thin film pattern 30a and the etching mask film pattern 40b are formed in the transfer pattern-forming region.
< Cross-sectional shape of transfer mask 100 >
The cross section of the transfer mask 100 thus obtained was observed by a scanning electron microscope.
The thin film pattern 30a for pattern formation of the transfer mask 100 of example 2 has a nearly vertical cross-sectional shape. Therefore, the thin film pattern 30a for pattern formation formed on the transfer mask 100 of example 2 has a cross-sectional shape that can sufficiently exhibit the phase shift effect.
From the above, it can be said that when the transfer mask 100 of example 2 is set on the mask stage of the exposure apparatus and the resist film transferred onto the substrate for the display apparatus is exposed, the transfer pattern including the fine pattern smaller than 2.0 μm can be transferred with high accuracy.
< Lightfastness >
A sample in which the thin film 30 for pattern formation used in the mask blank 10 of example 2 was formed on the light-transmissive substrate 20 was prepared. The film 30 for patterning of the sample of example 2 was irradiated with light of a metal halide light source including ultraviolet rays having a wavelength of 405nm so that the total irradiation amount was 10kJ/cm 2. The light resistance of the film 30 for pattern formation was evaluated by measuring the transmittance before and after the predetermined ultraviolet irradiation and calculating the change in the transmittance [ (transmittance after the ultraviolet irradiation) - (transmittance before the ultraviolet irradiation) ]. The transmittance was measured using a spectrophotometer.
As shown in fig. 7, in example 2, the change in transmittance before and after ultraviolet irradiation was good, and was 0.42%. From the above, the film for pattern formation of example 2 was a film having sufficiently high light resistance in practical use.
From the above, it is clear that the film for pattern formation of example 2 is an unprecedented excellent film satisfying the requirements of desired optical characteristics (transmittance, retardation) and high light resistance to exposure light including wavelengths in the ultraviolet region.
Example 3
The mask blank 10 of example 3 was manufactured in the same manner as the mask blank 10 of example 1, except that the thin film 30 for patterning was formed as described below.
The method for forming the thin film 30 for pattern formation of example 3 is as follows.
In order to form the thin film 30 for patterning on the main surface of the light-transmissive substrate 20, first, a mixed gas composed of argon (Ar) gas and nitrogen (N 2) gas is introduced into the first chamber. In example 3, the flow ratio (N 2/Ar) of nitrogen (N 2) to argon (Ar) was 1.111. Then, using a first sputtering target containing titanium and silicon, a nitride of titanium silicide containing titanium, silicon, and nitrogen is deposited on the main surface of the light-transmitting substrate 20 by reactive sputtering. Thus, a thin film 30 for pattern formation having a film thickness of 142nm was formed using titanium silicide nitride as a material. The composition of the film 30 in example 3 is substantially the same as that of the film 30 in example 1. The ratio of the titanium content to the total content of titanium and silicon in the thin film 30 for forming a pattern is 0.05 or more.
Then, the etching mask film 40 was formed in the same manner as in example 1.
Further, another thin film for patterning was formed on the main surface of another synthetic quartz substrate under the same film formation conditions as in example 3. Next, as for a sample obtained by cutting the thin film for patterning on the other synthetic quartz substrate into a predetermined size, an X-ray absorption microstructure analysis was performed by the X-ray absorption spectrometry (electron yield method) in the same manner as in example 1, and an X-ray absorption spectrum was obtained.
As shown in fig. 5, the X-ray absorption spectrum of example 3 has a front-side structure in a range of 400eV to 402eV, and has an absorption side in a range of 403eV to 406 eV. The shape of the X-ray absorption spectrum in example 3 has similar characteristics to the shape of the X-ray absorption spectrum in example 1.
As is found from the values shown in fig. 5 and 6, IA/IP in example 3 is 1.363 (IA is an X-ray absorption coefficient when the incident X-ray energy is 405.1eV in example 3, IP is an X-ray absorption coefficient when the incident X-ray energy is 401.0 eV) and satisfies a relationship of 1.45 or less.
Determination of transmittance and phase Difference
The transmittance (wavelength: 405 nm) and the retardation (wavelength: 405 nm) of the surface of the thin film 30 for patterning of the mask blank 10 of example 3 were measured. As a result, the film 30 for pattern formation in example 3 had a transmittance of 29.1% and a phase difference of 180 degrees.
Mask 100 for transfer and method for manufacturing the same
Using the mask blank 10 of example 3 manufactured as described above, the transfer mask 100 was manufactured in the same manner as in example 1, and the transfer mask 100 of example 3 was obtained as described above: on the light-transmitting substrate 20, a pattern-forming thin film pattern 30a having an aperture of 1.5 μm and a light-shielding tape having a laminated structure of the pattern-forming thin film pattern 30a and the etching mask film pattern 40b are formed in the transfer pattern-forming region.
< Cross-sectional shape of transfer mask 100 >
The cross section of the transfer mask 100 thus obtained was observed by a scanning electron microscope.
The thin film pattern 30a for pattern formation of the transfer mask 100 of example 3 has a nearly vertical cross-sectional shape. Therefore, the thin film pattern 30a for pattern formation formed on the transfer mask 100 of example 3 has a cross-sectional shape that can sufficiently exhibit the phase shift effect.
From the above, it can be said that when the transfer mask 100 of example 3 is set on the mask stage of the exposure apparatus and the resist film transferred onto the substrate for the display apparatus is exposed, the transfer pattern including the fine pattern smaller than 2.0 μm can be transferred with high accuracy.
< Lightfastness >
A sample in which the thin film 30 for pattern formation used in the mask blank 10 of example 3 was formed on the light-transmissive substrate 20 was prepared. The film 30 for patterning of the sample of example 3 was irradiated with light of a metal halide light source including ultraviolet rays having a wavelength of 405nm so that the total irradiation amount was 10kJ/cm 2. The light resistance of the film 30 for pattern formation was evaluated by measuring the transmittance before and after the predetermined ultraviolet irradiation and calculating the change in the transmittance [ (transmittance after the ultraviolet irradiation) - (transmittance before the ultraviolet irradiation) ]. The transmittance was measured using a spectrophotometer.
As shown in fig. 7, in example 3, the change in transmittance before and after ultraviolet irradiation was good, and was 0.36%. From the above, the film for pattern formation of example 3 was a film having sufficiently high light resistance in practical use.
From the above, it is clear that the film for pattern formation of example 3 is an unprecedented excellent film satisfying the requirements of desired optical characteristics (transmittance, retardation) and high light resistance to exposure light including wavelengths in the ultraviolet region.
Comparative example 1
The mask blank 10 of comparative example 1 was manufactured by the same procedure as the mask blank 10 of example 1, except that the thin film 30 for patterning was formed as described below.
The method for forming the thin film 30 for pattern formation of comparative example 1 is as follows.
In order to form the thin film 30 for patterning on the main surface of the light-transmissive substrate 20, first, a mixed gas composed of argon (Ar) gas and nitrogen (N 2) gas is introduced into the first chamber. In comparative example 1, the flow ratio (N 2/Ar) of nitrogen (N 2) to argon (Ar) was 0.393. Then, using a first sputtering target containing titanium and silicon, a nitride of titanium silicide containing titanium, silicon, and nitrogen is deposited on the main surface of the light-transmitting substrate 20 by reactive sputtering. Thus, a film 30 for pattern formation having a film thickness of 118nm and containing a nitride of titanium silicide (Ti: si: N: O=11.1:34.0:50.7:4.2 atomic%) was formed. Thus, the composition of the film 30 in comparative example 1 was substantially the same as that of the film 30 in example 1.
Then, the etching mask film 40 was formed in the same manner as in example 1.
Then, another thin film for pattern formation was formed on the main surface of the other synthetic quartz substrate under the same film formation conditions as in comparative example 1. Next, as for a sample obtained by cutting the thin film for patterning on the other synthetic quartz substrate into a predetermined size, an X-ray absorption microstructure analysis was performed by the X-ray absorption spectrometry (electron yield method) in the same manner as in example 1, and an X-ray absorption spectrum was obtained.
As shown in fig. 5, the X-ray absorption spectrum of comparative example 1 has an absorption edge in a range of from 403eV to 406eV of incident X-ray energy, but does not have a structure before edge (substantially monotonously increases) in a range of from 400eV to 402eV of incident X-ray energy.
As shown in fig. 6, the shape of the X-ray absorption spectrum in the vicinity of the structure before the edge in comparative example 1 is greatly different from that in example 1.
As determined from the values shown in fig. 5 and 6, the IA/IP in comparative example 1 was 1.543 (IA is the X-ray absorption coefficient when the incident X-ray energy is 405.0eV, IP is the X-ray absorption coefficient when the incident X-ray energy is 401.0eV in comparative example 1), and the relationship of 1.45 or less was not satisfied.
Determination of transmittance and phase Difference
The transmittance (wavelength: 405 nm) and the phase difference (wavelength: 405 nm) of the surface of the thin film 30 for patterning of the mask blank 10 of comparative example 1 were measured. As a result, the film 30 for pattern formation in comparative example 1 had a transmittance of 31.7% and a phase difference of 154 degrees.
Mask 100 for transfer and method for manufacturing the same
Using the mask blank 10 of comparative example 1 manufactured as described above, a transfer mask 100 was manufactured in the same manner as in example 1, and such a transfer mask 100 of comparative example 1 was obtained: on the light-transmitting substrate 20, a pattern-forming thin film pattern 30a having an aperture of 1.5 μm and a light-shielding tape composed of a laminated structure of the pattern-forming thin film pattern 30a and the etching mask film pattern 40b are formed in the transfer pattern-forming region.
< Cross-sectional shape of transfer mask 100 >
The cross section of the transfer mask 100 thus obtained was observed by a scanning electron microscope.
The thin film pattern 30a for pattern formation of the transfer mask 100 of comparative example 1 has a nearly vertical cross-sectional shape. Therefore, the thin film pattern 30a for pattern formation formed on the transfer mask 100 of comparative example 1 has a cross-sectional shape that can sufficiently exhibit the phase shift effect.
From the above, it can be said that when the transfer mask 100 of comparative example 1 is set on the mask stage of the exposure apparatus and the resist film transferred onto the substrate for the display apparatus is exposed, the transfer pattern including the fine pattern smaller than 2.0 μm can be transferred with high accuracy.
< Lightfastness >
A sample in which a thin film 30 for pattern formation used in the mask blank 10 of comparative example 1 was formed on a light-transmissive substrate 20 was prepared. The film 30 for patterning of the sample of comparative example 1 was irradiated with light of a metal halide light source including ultraviolet rays having a wavelength of 405nm so that the total irradiation amount was 10kJ/cm 2. The light resistance of the film 30 for pattern formation was evaluated by measuring the transmittance before and after the predetermined ultraviolet irradiation and calculating the change in the transmittance [ (transmittance after the ultraviolet irradiation) - (transmittance before the ultraviolet irradiation) ]. The transmittance was measured using a spectrophotometer.
As shown in fig. 7, in comparative example 1, the change in transmittance before and after ultraviolet irradiation was 2.32%, which exceeded the allowable range (within 2%). From the above, it was found that the film for pattern formation of comparative example 1 did not have sufficient light resistance for practical use.
Comparative example 2
The mask blank 10 of comparative example 2 was manufactured by the same procedure as the mask blank 10 of example 1, except that the thin film 30 for patterning was formed as described below.
The method for forming the thin film 30 for pattern formation of comparative example 2 is as follows.
In order to form the thin film 30 for patterning on the main surface of the light-transmissive substrate 20, first, a mixed gas composed of argon (Ar) gas and nitrogen (N 2) gas is introduced into the first chamber. In comparative example 2, the flow ratio (N 2/Ar) of nitrogen (N 2) to argon (Ar) was 0.383. Then, using a first sputtering target containing titanium and silicon, a nitride of titanium silicide containing titanium, silicon, and nitrogen is deposited on the main surface of the light-transmitting substrate 20 by reactive sputtering. Thus, a thin film 30 for pattern formation having a film thickness of 180nm and made of titanium silicide nitride (Ti: si: N: o=12.1:35.5:50.3:2.1 atomic%) was formed. The composition of the film 30 in comparative example 2 was substantially the same as that of the film 30 in example 1.
Then, the etching mask film 40 was formed in the same manner as in example 1.
Further, another thin film for patterning was formed on the main surface of the other synthetic quartz substrate under the same film formation conditions as in comparative example 2. Next, as for a sample obtained by cutting the thin film for patterning on the other synthetic quartz substrate into a predetermined size, an X-ray absorption microstructure analysis was performed by the X-ray absorption spectrometry (electron yield method) in the same manner as in example 1, and an X-ray absorption spectrum was obtained.
As shown in fig. 5, the X-ray absorption spectrum of comparative example 2 has an absorption edge in a range of from 403eV to 406eV of incident X-ray energy, but does not have a structure before edge (substantially monotonously increases) in a range of from 400eV to 402eV of incident X-ray energy.
As shown in fig. 6, the shape of the X-ray absorption spectrum in the vicinity of the structure before the edge in comparative example 2 is greatly different from that in example 1.
As is found from the values shown in fig. 5 and 6, the IA/IP in comparative example 2 is 1.478 (in comparative example 2, IA is an X-ray absorption coefficient when the incident X-ray energy is 404.7eV, and IP is an X-ray absorption coefficient when the incident X-ray energy is 401.0 eV), and does not satisfy the relation of 1.45 or less.
Determination of transmittance and phase Difference
The transmittance (wavelength: 405 nm) and the phase difference (wavelength: 405 nm) of the surface of the thin film 30 for patterning of the mask blank 10 of comparative example 2 were measured. As a result, the film 30 for pattern formation in comparative example 2 had a transmittance of 21.2% and a retardation of 235 degrees.
Mask 100 for transfer and method for manufacturing the same
Using the mask blank 10 of comparative example 2 manufactured as described above, the transfer mask 100 was manufactured in the same manner as in example 1, and the transfer mask 100 of comparative example 2 was obtained: on the light-transmitting substrate 20, a pattern-forming thin film pattern 30a having an aperture of 1.5 μm and a light-shielding tape having a laminated structure of the pattern-forming thin film pattern 30a and the etching mask film pattern 40b are formed in the transfer pattern-forming region.
< Cross-sectional shape of transfer mask 100 >
The cross section of the transfer mask 100 thus obtained was observed by a scanning electron microscope.
The thin film pattern 30a for pattern formation of the transfer mask 100 of comparative example 2 has a nearly vertical cross-sectional shape. Therefore, the thin film pattern 30a for pattern formation formed on the transfer mask 100 of comparative example 2 has a cross-sectional shape that can sufficiently exhibit the phase shift effect.
From the above, it can be said that when the transfer mask 100 of comparative example 2 is set on the mask stage of the exposure apparatus and the resist film transferred onto the substrate for the display apparatus is exposed, the transfer pattern including the fine pattern smaller than 2.0 μm can be transferred with high accuracy.
< Lightfastness >
A sample in which a thin film 30 for pattern formation used in the mask blank 10 of comparative example 2 was formed on a light-transmissive substrate 20 was prepared. The film 30 for patterning of the sample of comparative example 2 was irradiated with light of a metal halide light source including ultraviolet rays having a wavelength of 405nm so that the total irradiation amount was 10kJ/cm 2. The light resistance of the film 30 for pattern formation was evaluated by measuring the transmittance before and after the predetermined ultraviolet irradiation and calculating the change in the transmittance [ (transmittance after the ultraviolet irradiation) - (transmittance before the ultraviolet irradiation) ]. The transmittance was measured using a spectrophotometer.
As shown in fig. 7, in comparative example 2, the change in transmittance before and after ultraviolet irradiation was 3.30%, which exceeded the allowable range (within 2%). From the above, it was found that the film for pattern formation of comparative example 2 did not have sufficient light resistance for practical use.
In the above-described embodiments, the example of the transfer mask 100 for manufacturing the display device and the mask blank 10 for manufacturing the transfer mask 100 for manufacturing the display device are described, but the present invention is not limited thereto. The mask blank 10 and/or the transfer mask 100 of the present invention can be applied to manufacturing of semiconductor devices, MEMS manufacturing, manufacturing of printed boards, and the like. The present invention can also be applied to a binary mask plate having a light shielding film as the thin film 30 for forming a pattern, and a binary mask having a light shielding film pattern.
In the above-described embodiment, the example in which the size of the light-transmitting substrate 20 is 1214 (1220 mm×1400mm×13 mm) was described, but the present invention is not limited thereto. In the case of the mask blank 10 for manufacturing a display device, a large (large-sized) light-transmitting substrate 20 is used, and the length of one side of the main surface is 300mm or more with respect to the size of the light-transmitting substrate 20. The size of the light-transmitting substrate 20 used in the mask blank 10 for manufacturing a display device is, for example, 330mm×450mm or more and 2280mm×3130mm or less.
In the case of the mask blank 10 for manufacturing a semiconductor device, MEMS, or printed circuit board, a small (small-sized) light-transmitting substrate 20 is used, and the length of one side of the light-transmitting substrate 20 is 9 inches or less with respect to the size of the light-transmitting substrate 20. The size of the light-transmitting substrate 20 used in the mask blank 10 for the above-mentioned application is, for example, 63.1mm×63.1mm or more and 228.6mm×228.6mm or less. In general, as the light-transmitting substrate 20 used for the transfer mask 100 for manufacturing a semiconductor device and for MEMS, a 6025 size (152 mm×152 mm) or a 5009 size (126.6 mm×126.6 mm) is used. In general, as the light-transmitting substrate 20 used for the transfer mask 100 for manufacturing a printed circuit board, a 7012 size (177.4 mm×177.4 mm) or a 9012 size (228.6 mm×228.6 mm) is used.
Claims (16)
1. A mask blank comprising a thin film for patterning on a light-transmitting substrate, characterized in that,
The film contains a transition metal and silicon,
The X-ray absorption spectrum of the film obtained by the X-ray absorption spectrum method has a front-side structure in a range of an incident X-ray energy of 400eV to 402 eV.
2. The mask plate according to claim 1, wherein,
The film has an X-ray absorption spectrum with an absorption edge in a range of an incident X-ray energy of 403eV or more and 406eV or less.
3. The mask plate according to claim 2, wherein,
When the maximum value of the X-ray absorption coefficient at the structure before the edge is IP and the maximum value of the X-ray absorption coefficient at the absorption edge is IA, the relation of IA/IP below 1.45 is satisfied.
4. The mask plate according to claim 1, wherein,
The film also contains nitrogen.
5. The mask plate according to claim 1, wherein,
The film contains at least titanium as the transition metal.
6. The mask plate according to claim 1, wherein,
The ratio of the content of the transition metal in the film to the total content of the transition metal and silicon is 0.05 or more.
7. The mask plate according to claim 1, wherein,
An etching mask film having a different etching selectivity with respect to the thin film is provided on the thin film.
8. The mask blank according to claim 7, wherein,
The etching mask film contains chromium.
9. A transfer mask comprising a film having a transfer pattern formed on a light-transmitting substrate,
The film contains a transition metal and silicon,
The X-ray absorption spectrum of the film obtained by the X-ray absorption spectrum method has a front-side structure in a range of an incident X-ray energy of 400eV to 402 eV.
10. The transfer mask according to claim 9, wherein,
The film has an X-ray absorption spectrum with an absorption edge in a range of an incident X-ray energy of 403eV or more and 406eV or less.
11. The transfer mask according to claim 10, wherein,
When the maximum value of the X-ray absorption coefficient at the structure before the edge is IP and the maximum value of the X-ray absorption coefficient at the absorption edge is IA, the relation of IA/IP below 1.45 is satisfied.
12. The transfer mask according to claim 9, wherein,
The film also contains nitrogen.
13. The transfer mask according to claim 9, wherein,
The film contains at least titanium as the transition metal.
14. The transfer mask according to claim 9, wherein,
The ratio of the content of the transition metal in the film to the total content of the transition metal and silicon is 0.05 or more.
15. A method for manufacturing a transfer mask, comprising the steps of:
Preparing the mask plate according to claim 7 or 8;
forming a resist film having a transfer pattern on the etching mask film;
wet etching is performed using the resist film as a mask, and a transfer pattern is formed on the etching mask film; and
Wet etching is performed using the etching mask film on which the transfer pattern is formed as a mask, and a transfer pattern is formed on the thin film.
16. A method for manufacturing a display device is characterized by comprising the following steps:
placing the transfer mask according to any one of claims 9 to 14 on a mask stage of an exposure apparatus; and
The transfer mask is irradiated with exposure light, and a transfer pattern is transferred to a resist film provided on a substrate for a display device.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2023035852A JP2024127025A (en) | 2023-03-08 | 2023-03-08 | Mask blank, transfer mask, method for manufacturing a transfer mask, and method for manufacturing a display device |
| JP2023-035852 | 2023-03-08 |
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| CN118625588A true CN118625588A (en) | 2024-09-10 |
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| CN202410233460.2A Pending CN118625588A (en) | 2023-03-08 | 2024-03-01 | Mask blank, transfer mask, method for manufacturing transfer mask, and method for manufacturing display device |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP2024127025A (en) |
| KR (1) | KR20240137470A (en) |
| CN (1) | CN118625588A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6730445B2 (en) | 2002-04-12 | 2004-05-04 | International Business Machines Corporation | Attenuated embedded phase shift photomask blanks |
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- 2023-03-08 JP JP2023035852A patent/JP2024127025A/en active Pending
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- 2024-02-28 KR KR1020240029100A patent/KR20240137470A/en unknown
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