CN109960105A - The manufacturing method of photomask blank and photomask, the manufacturing method of display device - Google Patents
The manufacturing method of photomask blank and photomask, the manufacturing method of display device Download PDFInfo
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- CN109960105A CN109960105A CN201811515759.8A CN201811515759A CN109960105A CN 109960105 A CN109960105 A CN 109960105A CN 201811515759 A CN201811515759 A CN 201811515759A CN 109960105 A CN109960105 A CN 109960105A
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- photomask
- inhibition layer
- film
- wavelength
- reflex inhibition
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 56
- 230000009153 reflex inhibition Effects 0.000 claims abstract description 193
- 239000000758 substrate Substances 0.000 claims abstract description 124
- 238000002310 reflectometry Methods 0.000 claims abstract description 100
- 239000000463 material Substances 0.000 claims abstract description 50
- 230000003287 optical effect Effects 0.000 claims abstract description 30
- 239000012780 transparent material Substances 0.000 claims abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 108
- 239000011651 chromium Substances 0.000 claims description 107
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 63
- 229910052804 chromium Inorganic materials 0.000 claims description 61
- 229910052757 nitrogen Inorganic materials 0.000 claims description 60
- 229910052760 oxygen Inorganic materials 0.000 claims description 50
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 41
- 239000001301 oxygen Substances 0.000 claims description 41
- 239000000203 mixture Substances 0.000 claims description 37
- 230000010363 phase shift Effects 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 26
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- 238000001579 optical reflectometry Methods 0.000 claims description 5
- 238000001228 spectrum Methods 0.000 claims description 4
- 238000005530 etching Methods 0.000 abstract description 51
- 239000007789 gas Substances 0.000 description 116
- 238000005477 sputtering target Methods 0.000 description 28
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 22
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 20
- 238000012546 transfer Methods 0.000 description 18
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
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- -1 that is Substances 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
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- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 229910016006 MoSi Inorganic materials 0.000 description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- SJKRCWUQJZIWQB-UHFFFAOYSA-N azane;chromium Chemical compound N.[Cr] SJKRCWUQJZIWQB-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001845 chromium compounds Chemical class 0.000 description 2
- 238000012790 confirmation Methods 0.000 description 2
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- 238000010586 diagram Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
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- 230000003628 erosive effect Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 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
- 229910052743 krypton Inorganic materials 0.000 description 2
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 2
- 230000001795 light effect Effects 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
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- 230000000149 penetrating effect Effects 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910008484 TiSi Inorganic materials 0.000 description 1
- 229910006249 ZrSi Inorganic materials 0.000 description 1
- QVGJMDYKGDOMOF-UHFFFAOYSA-N [O].[O].[OH-].[NH4+] Chemical compound [O].[O].[OH-].[NH4+] QVGJMDYKGDOMOF-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
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- 238000005520 cutting process Methods 0.000 description 1
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- 208000002173 dizziness Diseases 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration 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
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- 238000009751 slip forming Methods 0.000 description 1
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- 238000010183 spectrum analysis Methods 0.000 description 1
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Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
- G03F1/26—Phase shift masks [PSM]; PSM blanks; Preparation thereof
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
- G03F1/26—Phase shift masks [PSM]; PSM blanks; Preparation thereof
- G03F1/32—Attenuating PSM [att-PSM], e.g. halftone PSM or PSM having semi-transparent phase shift portion; 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
- G03F1/38—Masks having auxiliary features, e.g. special coatings or marks for alignment or testing; Preparation thereof
- G03F1/46—Antireflective coatings
Abstract
The present invention provides a kind of photomask blank, meets following optical characteristics, that is, high-precision mask pattern can be obtained when making photomask by etching, also, be able to suppress display unevenly when making display device using photomask.Photomask blank is used when making display device manufacture photomask, comprising: transparent substrate, by being constituted for the exposure substantially transparent material of light；Photomask, it is set on transparent substrate, by being constituted for the exposure substantially opaque material of light, photomask has the first reflex inhibition layer, light shield layer, the second reflex inhibition layer from transparent substrate side, the face of photomask side in the two sides using photomask blank as surface, using the face of transparent substrate side as when the back side, in the range of exposure wavelength is 365nm~436nm, for expose light surface reflectivity and backside reflection rate be respectively 10% hereinafter, and the backside reflection rate in the wave-length coverage wavelength dependency be 5% or less.
Description
Technical field
The present invention relates to the manufacturing methods of photomask blank and photomask, the manufacturing method of display device.
Background technique
With LCD (liquid crystal display device, Liquid Crystal Display) be representative FPD (panel display apparatus,
Flat Panel Display) etc. in display devices, high-resolution, high speed displayization and large screen, big visual angleization are fast together
Speed development.The high-resolution, the required element of high speed displayization first is that the electricity such as fine and high dimensional accuracy element, wiring
The production of sub-circuit pattern.When being patterned to such display device with electronic circuit, photoetching process is mostly used greatly.Therefore, it needs
Imperceptibly to be formed with the display device manufacture photomask of patterns of high precision.
Display device manufacture is made of photomask by photomask blank.Photomask blank passes through by synthetic quartz glass etc.
It is arranged on the transparent substrate of composition by being constituted for exposing the photomask that the opaque material of light is constituted.In photomask blank or
In photomask, in order to inhibit light reflection when exposure, reflex inhibition layer, photomask blank are set in the front and back sides side of photomask
Such as the film knot for being sequentially laminated with the first reflex inhibition layer, light shield layer and the second reflex inhibition layer from transparent substrate side
Structure.Photomask forms defined mask pattern to the photomask composition of photomask blank by using wet etching etc. to make
Out.
This display device manufacture photomask, as its master photomask blank and with the manufacturing method of the two
Relevant technology is disclosed in patent document 1.
Existing technical literature
Patent document
Patent document 1: Korean granted patent 10-1473163 bulletin
Summary of the invention
In the manufacture of display device (for example, TV display panel), for example, using photomask to base board for display device
Predetermined pattern is transferred, then slides base board for display device, then transfer predetermined pattern, so repeatedly carries out pattern transfer.
In the transfer, because exposure light is from the light source of exposure device to the shadow of the reflected light of photomask back side when photomask incidence
Ring, or because expose light pass through photomask and from transfer printing body reflect due to return to photomask surface side reflected light influence,
Irradiation is more than expected exposure light near the coincidence part of display device sometimes.As a result, adjacent pattern is each other with a part
The mode of overlapping is exposed, and it is uneven that display is generated in the display device produced.In particular in display device manufacture
Photomask enlargement, often use broadband light (complex light comprising the different a variety of light of wavelength) as expose light, deposit
In the uneven more significant tendency of display.
Therefore, in photomask blank, in order to inhibit display uneven, it is desirable that set the reflectivity at the table back side of photomask
For 10% or less (for example, wavelength 365nm~436nm), further preferably require to be set as 5% or less (for example, 400nm~
436nm).In turn, from the viewpoint of the CD uniformity (CD Uniformity) for improving photomask, when in view of laser description
Light is in the surface reflection of photomask, it is desirable that the reflectivity of shading film surface is set as 5% or less (for example, wavelength 413nm), into
One step preferably requires to be set as 3% or less (for example, wavelength 413nm).
In addition, about display device manufacture photomask, in addition to the high-resolution to display device, high speed displayization are wanted
Other than asking, also require the enlargement for promoting substrate size, in recent years, use the rectangular substrate that bond length is 850mm or more
Ultra-large type photomask is used in the manufacture of display device.In addition, the large-scale light for being 850mm or more as above-mentioned bond length
Mask has G7 850mm × 1200mm size, G8 1220mm × 1400mm size, G10 1620mm × 1780mm size,
Especially as the CD uniformity of the mask pattern of this large-scale photomask, it is desirable that 100nm high-precision mask pattern below.
In the photomask blank of existing patent document 1, in the situation that the bond length of substrate is set as to 850mm or more
Under, photomask will be used by not being able to satisfy while the reflectivity at the table back side of photomask is set as 10% or less for exposure wavelength
The CD uniformity of the mask pattern for the photomask that blank is produced is set as 100nm requirement below.
The purpose of the present invention is to provide a kind of photomask blanks, can obtain when having produced photomask by etching
To high-precision mask pattern, and meets and be able to suppress display non-uniform optics spy when making display device using photomask
Property.
(scheme 1)
A kind of photomask blank is used when making display device manufacture photomask, it is characterized in that, comprising: it is transparent
Substrate, by being constituted for the exposure substantially transparent material of light；Photomask is set on the transparent substrate, by for described
The substantially opaque material of light is exposed to constitute, the photomask have from the transparent substrate side the first reflex inhibition layer,
Light shield layer, the second reflex inhibition layer, using the face of the photomask side in the two sides of the photomask blank as surface, general
When the face of the transparent substrate side is as the back side, in the range of exposure wavelength is 365nm~436nm, for the exposure light
Surface reflectivity and backside reflection rate be respectively 10% hereinafter, and the backside reflection rate in the wave-length coverage wave
Long dependence is 5% or less.
(scheme 2)
Photomask blank as described in scheme 1, it is characterized in that, it is whole in the range of exposure wavelength is 365nm~436nm
A region, the backside reflection rate are smaller than the surface reflectivity.
(scheme 3)
Photomask blank as described in scheme 1 or 2, it is characterized in that, with the surface reflection of the photomask blank
Rate and the backside reflection rate as the longitudinal axis and using wavelength as the reflectance spectrum of horizontal axis in, be 300nm~500nm in wavelength
Wave band in, the reflectance spectrum at the surface and the back side is downwardly convex curve respectively, with the surface reflection
The corresponding wavelength of the minimum value of rate and the backside reflection rate, that is, bottom peak (bottom peak) is located at 350nm~450nm.
(scheme 4)
Photomask blank as described in any one of scheme 1~3, it is characterized in that, it is 365nm~436nm in exposure wavelength
In the range of, the wavelength dependency of the backside reflection rate is smaller than the wavelength dependency of the surface reflectivity.
(scheme 5)
Photomask blank as described in any one of scheme 1~4, it is characterized in that, in the wave-length coverage of 530nm or more,
The surface reflectivity is 10% or more.
(scheme 6)
Photomask blank as described in any one of scheme 1~5, it is characterized in that,
First reflex inhibition layer is the chromium based material containing chromium, oxygen and nitrogen, and the containing ratio with chromium is 25~75 former
Sub- %, oxygen containing ratio be 15~45 atom %, the composition that the containing ratio of nitrogen is 10~30 atom %,
The light shield layer is chromium based material containing chromium and nitrogen, and the containing ratio with chromium is 70~95 atom %, nitrogen contains
It is forming for 5~30 atom % by rate,
Second reflex inhibition layer is the chromium based material containing chromium, oxygen and nitrogen, and the containing ratio with chromium is 30~75 former
Sub- %, oxygen containing ratio be 20~50 atom %, the composition that the containing ratio of nitrogen is 5~20 atom %.
(scheme 7)
Photomask blank as described in scheme 6, it is characterized in that,
In first reflex inhibition layer, the containing ratio of chromium is 50~75 atom %, and the containing ratio of oxygen is 15~35 former
Sub- %, the containing ratio of nitrogen are 10~25 atom %,
In second reflex inhibition layer, the containing ratio of chromium is 50~75 atom %, and the containing ratio of oxygen is 20~40 former
Sub- %, the containing ratio of nitrogen are 5~20 atom %.
(scheme 8)
Photomask blank as described in scheme 6 or 7, it is characterized in that, the containing ratio ratio of the oxygen of second reflex inhibition layer
First reflex inhibition layer is high.
(scheme 9)
Photomask blank as described in scheme 6 or 7, it is characterized in that, the containing ratio ratio of the nitrogen of first reflex inhibition layer
Second reflex inhibition layer is high.
(scheme 10)
Photomask blank as described in any one of scheme 1~9, it is characterized in that, the transparent substrate is rectangular substrate, should
The bond length of substrate is 850mm or more 1620mm or less.
(scheme 11)
Photomask blank as described in any one of scheme 1~10, it is characterized in that, in the transparent substrate and the shading
Semi-transparent film is also equipped between film, the semi-transparent film has the optical concentration lower than the optical concentration of the photomask.
(scheme 12)
Photomask blank as described in any one of scheme 1~10, it is characterized in that, in the transparent substrate and the shading
The phase shift film for making the phase shift of transmitted light is also equipped between film.
(scheme 13)
A kind of manufacturing method of photomask, which is characterized in that comprise the following steps:
The photomask blank described in any one of preparation scheme 1~10；
Etchant resist is formed on the photomask, using the corrosion-resisting pattern that is formed by the etchant resist as mask to the screening
Light film is etched, and shading film figure is formed on the transparent substrate.
(scheme 14)
A kind of manufacturing method of photomask, which is characterized in that comprise the following steps:
The photomask blank described in preparation scheme 11；
Etchant resist is formed on the photomask, using the corrosion-resisting pattern that is formed by the etchant resist as mask to the screening
Light film is etched, and shading film figure is formed on the transparent substrate；
The semi-transparent film is etched using the shading film figure as mask, forms half on the transparent substrate
Light transmission film figure.
(scheme 15)
A kind of manufacturing method of photomask, which is characterized in that comprise the following steps:
The photomask blank described in preparation scheme 12；
Etchant resist is formed on the photomask, using the corrosion-resisting pattern that is formed by the etchant resist as mask to the screening
Light film is etched, and shading film figure is formed on the transparent substrate；
The phase shift film is etched using the shading film figure as mask, forms phase shift on the transparent substrate
Film figure.
(scheme 16)
A kind of manufacturing method of display device, which is characterized in that there is exposure process, it, will be by the exposure process
The photomask that the manufacturing method of photomask described in any one of scheme 13~15 obtains is positioned in the mask carrying stage of exposure device
On, will be formed in the shading film figure on the photomask, the semi-transparent film figure, in the phase shift film figure extremely
Few mask pattern exposure is transferred on the resist being formed on display device substrate.
In accordance with the invention it is possible to which it is excellent and have and can press down in the manufacture of display device to obtain can producing pattern accuracy
System shows the photomask blank of the photomask of non-uniform optical characteristics.
Detailed description of the invention
Fig. 1 is the sectional view for indicating the outline structure of photomask blank of an embodiment of the present invention.
Fig. 2 is the figure for indicating the composition analysis result of the photomask blank of embodiment 1 on film thickness direction.
Fig. 3 is the figure for indicating the reflectance spectrum at the table back side of the photomask blank of embodiment 1.
Fig. 4 is the section shape for the shading film figure to the photomask for using the photomask blank of embodiment 1 to produce
The figure that the characteristic of shape is illustrated.
Fig. 5 is the schematic diagram for being illustrated to film forming mode when forming photomask by reactive sputtering.
Description of symbols
1 photomask blank
11 transparent substrates
12 photomasks
13 first reflex inhibition layers
14 light shield layers
15 second reflex inhibition layers
Specific embodiment
The present inventor is uneven in order to inhibit display when producing display device using existing photomask, covers to light emphatically
The face (hereinafter also referred to as surface) of the photomask side of mould and face (hereinafter also referred to as the back side) respective reflection of transparent substrate side
Rate spectrum is studied.Each reflectance spectrum at the table back side is that reflectivity is different according to different wave length, and reflectivity is in spy
The downwardly convex curve of standing wave section minimalization.When having studied the correlation between the reflectance spectrum and display unevenly
It was found that in the range of exposure wavelength is 365nm~436nm, if surface reflectivity and backside reflection rate is small and the back side
The wavelength dependency of reflectivity is small, it will be able to it is uneven to further suppress display.
What the wavelength dependency of reflectivity indicated is the variation that reflectivity relies on exposure wavelength, and wavelength dependency is small to indicate anti-
The difference of the maximum value and minimum value of penetrating rate is small, that is, the variable quantity (fluctuating range) of reflectivity is small.
Up to the present, when using photomask to being transferred substrate irradiation exposure light and carrying out pattern transfer, only consider
The situation for being transferred the variation of pattern accuracy caused by substrate is transferred to as the light of reflex exposure again of shading film surface to inhibition.
Therefore, surface reflectivity is only accounted for, backside reflection rate is not accounted for.
But according to the present invention people research it is found that using photomask projection exposure in, with from be formed with it is photic
The shadow for the dazzle that the reflected light for being transferred substrate of resist is repeatedly generated in the photomask patterned surfaces reflection of photomask
Sound is compared, and is exposed after the optical system reflection of device (transfer device) by the reflected light at the back side from shading film figure again
The return light for being incident on photomask is bigger on influencing caused by transfer pattern accuracy, it is easier to it is uneven to generate display.This be because
For with the enlargement of photomask, the miniaturization of pattern and High precision, the reflectivity at the back side from shading film figure is previous
It becomes much larger, this is the factor being realized for the first time.Especially when display panel makes, used shading film figure is opened
In photomask (for example, ITO pattern, slit-shaped pattern) of the mouth rate lower than 50%, the back side of shading film figure in photomask
The influence of reflected light increase, it is uneven that display is easy to produce in the display panel made using photomask.
Because backside reflection rate unevenly brings greater impact display, the present inventor is from surface reflectivity and back
Face reflectivity sets out, and is studied mask blank.It finds in the course of the research, is not only the reflectivity at the table back side, and
The wavelength dependency of backside reflection rate also influences whether that the precision of transfer pattern and display are uneven.Moreover, further study
As a result, it has been found that anti-to the surface of exposure light in the range of exposure wavelength is 365nm~436nm by being arranged to mask blank
Penetrate rate and backside reflection rate be respectively 10% or less and the wavelength dependency of backside reflection rate be 5% hereinafter, being covered producing light
When mould, the reflected light that can be effectively reduced the back side from its shading film figure is exposed the optical system of device (transfer device)
The return light of photomask is again incident on after system reflection, compared with the case where using existing photomask production display device, energy
It is enough to inhibit display uneven.
The present invention is to be found and completed based on the studies above.
In the following, embodiments of the present invention are specifically described referring to attached drawing.In addition, following implementation is to send out this
One mode of bright materialization, the present invention are not limited in the range.In addition, in the accompanying drawings, in same or comparable part
Same symbol is marked, simplify or is omitted the description.
< photomask blank >
In the following, the photomask blank to an embodiment of the present invention is illustrated.The photomask blank of present embodiment exists
It is used when making display device manufacture photomask, the photomask is for example with the Single wavelength for being selected from 365nm~436nm wave band
Light or answering with light (for example, i line (wavelength 365nm), h line (405nm), g line (wavelength 436nm)) comprising multiple wavelength
Light combination is exposed.In addition, being under the numerical value recorded with "~" front and back is with the numberical range that "~" indicates in the present specification
Limit value and upper limit value and include these values range.
Fig. 1 is the sectional view for indicating the outline structure of photomask blank of an embodiment of the present invention.Photomask blank 1 wraps
It is constituted containing transparent substrate 11 and photomask 12.In the following, the photomask blank as an embodiment of the present invention, to photomask
Mask pattern (transfer pattern) is that the dualistic formula photomask blank of shading film figure is illustrated.
(transparent substrate)
As long as transparent substrate 11 is by forming the exposure substantially transparent material of light and having the substrate of translucency, just
It is not particularly limited.As the transmitance to exposure wavelength, the baseplate material of 85% or more, preferably 90% or more can be used.
As the material of formation transparent substrate 11, such as synthetic quartz glass, soda-lime glass, alkali-free glass, low thermal expansion glass can be enumerated
Glass.
The size of transparent substrate 11 size required by manufacture photomask can be suitably changed according to the display device.Example
Such as, rectangular substrate can be used as transparent substrate 11, is the transparent base that bond length is 330mm or more 1620mm size below
Plate 11.As transparent substrate 11, for example, can be used size be 330mm × 450mm, 390mm × 610mm, 500mm × 750mm,
520mm×610mm、520mm×800mm、800×920mm、850mm×1200mm、850mm×1400mm、1220mm×
The substrate of 1400mm, 1620mm × 1780mm etc..It is particularly preferred that the bond length of substrate is 850mm or more 1620mm or less.
By using this transparent substrate 11, the display device manufacture photomask of G7~G10 can be obtained.
(photomask)
Photomask 12 is anti-by stacking gradually the first reflex inhibition layer 13, light shield layer 14 and second from 11 side of transparent substrate
It penetrates inhibition layer 15 and constitutes.In addition, in the following illustration, using the face of 12 side of photomask in the two sides of photomask blank 1 as
Surface is illustrated using the face of 11 side of transparent substrate as the back side.
First reflex inhibition layer 13 is set to the face of the side close to transparent substrate 11 of light shield layer 14 in photomask 12
On, it is configured in the case where carrying out pattern transfer using the photomask produced by photomask blank 1 close to exposure device and (is exposed
Radiant) side.In the case where being exposed processing using photomask, from 11 side of transparent substrate (back side) of photomask
Irradiation exposure light transfers pattern on the etchant resist being formed on transfer printing body i.e. base board for display device and transfers picture.At this moment, it exposes
Reflected light of the light light after the back side lateral reflection of shading film figure is incident on the optical system of exposure device, then covers again from light
11 side of transparent substrate of mould is incident, to become shading film figure, that is, mask pattern stray light, leads to the formation of ghost image and dizzy
Increase of light quantity etc. transfer picture deterioration, or because base board for display device coincidence part nearby irradiate exceed expected from expose light
And it is uneven to generate display.When carrying out pattern transfer using photomask, the first reflex inhibition layer 13 is due to being able to suppress exposure
Light therefore helps to inhibit the deterioration of transfer picture and the raising of transferring properties, also, energy in the reflection of the back side of photomask 12
It is enough to inhibit to occur near the coincidence part of base board for display device to cause display uneven because of exposure light expected from irradiation exceeds.
Light shield layer 14 is being set between the first reflex inhibition layer 13 and the second reflex inhibition layer 15 in photomask 12.Shading
Layer 14 has regulatory function, has photomask 12 for exposing the substantially opaque optical concentration of light.Here, for exposure
Light is substantially opaque to refer to that optical concentration is 3.0 or more light-proofness, and from the viewpoint of transferring properties, optical concentration is preferred
It is 4.0 or more, further preferably 4.5 or more.
Second reflex inhibition layer 15 is set to the face of the side of the separate transparent substrate 11 of light shield layer 14 in photomask 12
On.Etchant resist is formed in the second reflex inhibition layer 15 and passes through drawing apparatus on the etchant resist (for example, laser description fills
Set) description light (laser) describe as defined in pattern when, the second reflex inhibition layer 15 is able to suppress the surface side of photomask 12
Reflection, therefore can be improved the CD uniformity (CD of corrosion-resisting pattern and the mask pattern formed based on the corrosion-resisting pattern
Uniformity).In addition, the second reflex inhibition layer 15 is configured at transfer printing body and shows dress in the case where being used as photomask
It sets and uses substrate-side, be able to suppress and returned again by the surface lateral reflection of the photomask of photomask 12 by the light of transfer printing body reflection
Transfer printing body inhibits the deterioration of transfer picture and facilitates the raisings of transferring properties, further, it is possible to inhibit in base board for display device
Coincidence part nearby occur to exceed because of irradiation expected from show caused by exposure light it is uneven.
(optical characteristics of photomask blank)
As described above, photomask blank 1 has for exposure light in the range of exposure wavelength is 365nm~436nm
Surface reflectivity and backside reflection rate be respectively 10% hereinafter, and backside reflection rate wavelength dependency be 5% optics below
Characteristic.Here, the wavelength dependency of backside reflection rate refers to that back side in the range of exposure wavelength is 365nm~436nm is anti-
Penetrate the maximum value of rate and the difference of minimum value.Specifically, the reflection on surface obtained from surface irradiation light to photomask blank 1
Rate spectrum, in the range of exposure wavelength is 365nm~436nm, surface reflectivity is 10% or less.It is in exposure wavelength
In the range of 365nm~436nm, surface reflectivity is preferably 7.5% hereinafter, further preferably 5% or less.In addition same
Ground, the rearwardly reflectance spectrum at the back side obtained from irradiation light, in the range of exposure wavelength is 365nm~436nm, the back side
Reflectivity is 10% or less.Exposure wavelength be 365nm~436nm wave-length coverage in, backside reflection rate be preferably 7.5% with
Under, further preferably 5% or less.Moreover, the wavelength dependency of backside reflection rate is 365nm~436nm's in exposure wavelength
It is 5% or less in range.In particular, using display when photomask production display device uneven to reduce, it is important that
The wavelength dependency of backside reflection rate is 5% or less in the range of exposure wavelength is 365nm~436nm.It is in exposure wavelength
In the wave-length coverage of 365nm~436nm, the wavelength dependency of backside reflection rate is preferably 3% or less.
Preferably, in the reflectance spectrum at the comparison sheet back side, in the range of exposure wavelength is 365nm~436nm
The backside reflection rate of whole region, photomask blank 1 is less than surface reflectivity.
In addition, when being able to suppress at more pieces of manufacture and show non-uniform photomask blank, in order to steadily with high yield
Rate is manufactured, photomask blank 1 using the surface reflectivity of photomask blank and backside reflection rate as the longitudinal axis, with wavelength be horizontal
In the reflectance spectrum of axis, the reflectance spectrum in the wave band that wavelength is 300nm~500nm is downwardly convex curve, with table
The corresponding wavelength of the minimum value (bottom peak) of face reflectivity and backside reflection rate is preferably placed in 350nm~450nm.
Additionally preferably, in the range of exposure wavelength is 365nm~436nm, the backside reflection rate of photomask blank 1
The wavelength dependency of wavelength dependency specific surface reflectivity is small.In turn, from the screening for the photomask for using photomask blank 1 to produce
From the aspect of the detection accuracy of the dimension measurement of photosensitiveness film figure, it is preferable that in the wave-length coverage of 530nm or more, photomask
The surface reflectivity of the photomask of blank 1 is 10% or more.
(material of photomask)
Next, being illustrated to the layers of material of photomask 12.
As long as layers of material can obtain above-mentioned optical characteristics in photomask blank 1, there is no particular limitation, but
From the aspect of obtaining above-mentioned optical characteristics, it is preferable to use following materials for each layer.
First reflex inhibition layer 13 is preferably made of the chromium based material containing chromium, oxygen and nitrogen.In first reflex inhibition layer 13
Oxygen can play reduce from back side exposure light reflectivity effect.In addition, the nitrogen in the first reflex inhibition layer 13 removes
It can play other than the effect for reducing the reflectivity of the light of the exposure from back side, can also enable and pass through etching using photomask blank
The section for the shading film figure that (especially wet etching) is formed is close vertical, and improves CD uniformity.In addition, being lost from control
From the aspect of carving characteristic, it can also further contain carbon, fluorine.
Light shield layer 14 is preferably made of the chromium based material containing chromium and nitrogen.Nitrogen in light shield layer 14 can reduce and the first reflection
Etching rate difference between inhibition layer 13, the second reflex inhibition layer 15 enables and passes through etching (especially wet type using photomask blank
Etching) section of shading film figure that is formed shortens the etching period of photomask 12 (entirety) close to vertical, and raising CD is equal
Even property.In addition, can also further contain aerobic, carbon, fluorine from the aspect of control etching characteristic.
Second reflex inhibition layer 15 is preferably made of the chromium based material containing chromium, oxygen and nitrogen.In second reflex inhibition layer 15
Oxygen can play reduce the drawing apparatus from surface side description light reflectivity and from table side exposure light reflectivity
Effect.In addition, the adaptation with etchant resist can be improved, inhibit by the etchant at the interface from etchant resist and photomask 12
Lateral erosion caused by infiltration.In addition, the nitrogen in the second reflex inhibition layer 15, which removes to play, reduces the light of the description from surface side
Other than the effect of the reflectivity of reflectivity and the exposure light from surface side, can also it enable (special by etching using photomask blank
It is not wet etching) section of shading film figure that is formed improves CD uniformity close to vertical.In addition, being etched from control
From the aspect of characteristic, it can also further contain carbon, fluorine.
(composition of photomask)
Next, each layer composition to photomask 12 is illustrated.In addition, it is to pass through that the containing ratio of aftermentioned each element, which is set,
The value that X-ray photoelectron spectroscopy (XPS) determines.
Photomask 12 is preferably constituted as follows, that is, presses containing ratio, the first reflex inhibition layer 13 contains 25~75 respectively
The chromium (Cr) of atom %, the oxygen (O) of 15~45 atom %, 10~30 atom % nitrogen (N), light shield layer 14 respectively contain 70~95
The nitrogen (N) of the chromium (Cr) of atom %, 5~30 atom %, chromium of second reflex inhibition layer 15 respectively containing 30~75 atom %
(Cr), the nitrogen (N) of the oxygen (O) of 20~50 atom %, 5~20 atom %.It is highly preferred that pressing containing ratio, the first reflex inhibition layer
The N of 13 Cr respectively containing 50~75 atom %, the O of 15~35 atom %, 5~25 atom %, the second reflex inhibition layer 15 are divided
The N of the O of Cr, 5~40 atom % not containing 50~75 atom %, 5~20 atom %.
Preferably, the first reflex inhibition layer 13 and the second reflex inhibition layer 15 are respectively provided at least any one member in O and N
The region of composition variation occurs continuously or stepwise along film thickness direction for the containing ratio of element.
The region that second reflex inhibition layer 15 preferably increases with O containing ratio towards 14 side of light shield layer of film thickness direction.
In addition, the area that the second reflex inhibition layer 15 preferably declines with N containing ratio towards 14 side of light shield layer of film thickness direction
Domain.
In addition, the first reflex inhibition layer 13 preferably has, the transparent substrate 11O containing ratio towards film thickness direction increases and N contains
The region for thering is rate to decline.
In addition, being carried on the back in photomask blank 1 and the photomask produced by the photomask blank 1 from table is further decreased
The reflectivity in face and from the viewpoint of reducing the difference of the two reflectivity, it is preferable that the O containing ratio ratio of the second reflex inhibition layer 15
First reflex inhibition layer 13 is high, and the N containing ratio of the first reflex inhibition layer 13 is higher than the second reflex inhibition layer 15.Specifically, excellent
Choosing makes the O containing ratio of the second reflex inhibition layer 15 than the big 5 atom atom of %~10 % or more of the first reflex inhibition layer 13, and preferably
Make the N containing ratio of the first reflex inhibition layer 13 than the big 5 atom atom of %~10 % or more of the second reflex inhibition layer 15.In addition, such as
Fruit the first reflex inhibition layer 13 or the second reflex inhibition layer 15 have composition tilting zone, and O containing ratio and N containing ratio indicate film
Mean concentration on thick direction.
In addition, in the first reflex inhibition layer 13, light shield layer 14 and the second reflex inhibition layer 15, the containing ratio of each element
Variation can continuous or step, but it is preferably continuous.
(about bond styles (chemical state))
Light shield layer 14 preferably comprises chromium (Cr) and dichromium nitride (Cr2N)。
First reflex inhibition layer 13, the second reflex inhibition layer 15 preferably comprise a chromium nitride (CrN), chromium oxide (III)
(Cr2O3), chromium oxide (VI) (CrO3)。
(about film thickness)
In photomask 12, the first reflex inhibition layer 13, light shield layer 14 and the respective thickness of the second reflex inhibition layer 15 do not have
It is particularly limited to, it can the optical concentration according to required by photomask 12 or reflectivity and appropriate adjustment.First reflex inhibition layer
As long as 13 thickness can play the light of the back side from photomask 12 by the anti-of the surface of the first reflex inhibition layer 13
The thickness of interference of light effect penetrated and realized by the reflection at the interface between the first reflex inhibition layer 13 and light shield layer 14.
On the other hand, as long as the thickness of the second reflex inhibition layer 15 can play by second the light of the surface side from photomask 12
The surface of reflex inhibition layer 15 reflection and realized by the reflection at the interface between the second reflex inhibition layer 15 and light shield layer 14
Interference of light effect thickness.As long as the thickness of light shield layer 14 can make the optical concentration of photomask 12 become 3 or more
Thickness.Specifically, in order to which the reflectivity at the table back side is set as 10% or less in photomask 12 and by optical concentration
3.0 or more are set as, such as the film thickness of the first reflex inhibition layer 13 can be set as 15nm~60nm, the film thickness of light shield layer 14 is set
For 50nm~120nm, the film thickness of the second reflex inhibition layer 15 is set as 10nm~60nm.
The manufacturing method > of < photomask blank
Next, being illustrated to the manufacturing method of above-mentioned photomask blank 1.
(preparatory process)
Prepare for exposing the substantially transparent transparent substrate 11 of light.In addition, transparent substrate 11 can be implemented to grind as needed
The arbitrary manufacturing procedure such as process, polishing process is cut, to become flat and smooth main surface.It can carry out after a polish
Cleaning removes the foreign matter or dirt on the surface of transparent substrate 11.As cleaning solution, such as it can be used sulfuric acid, dioxysulfate water mixed
Close liquid (SPM), ammonium hydroxide, ammonium hydroxide dioxygen water mixed liquid (APM), OH free radical ejected wash water, Ozone Water, warm water etc..
(formation process of the first reflex inhibition layer)
Next, forming the first reflex inhibition layer 13 on transparent substrate 11.The formation by reactive sputtering carry out at
Film, reactive sputtering using the sputtering target material containing Cr and comprising containing aerobic system's gas, nitrogen system gas reactant gas with it is dilute
There is the sputter gas of gas.At this moment, as membrance casting condition, the flow that reactant gas contained by sputter gas may be selected becomes gold
The flow of category mode.
Here, being illustrated using Fig. 5 to metal mode.When Fig. 5 is for film is formed by reactive sputtering
The schematic diagram that film forming mode is illustrated, what horizontal axis indicated is the reactivity in the mixed gas of rare gas and reactant gas
Partial pressure (flow) ratio of gas, the voltage for being applied to target that the longitudinal axis indicates.In reactive sputtering, oxygen system gas is being imported
When having carried out electric discharge to target while body, nitrogen system gas isoreactivity gas, the state of discharge plasma can be with reaction
The flow of property gas and change, therewith, film forming speed can change.Because of the difference of the film forming speed, 3 modes are co-existed in.
Specifically, as shown in figure 5, in the presence of the big Mr. Yu's threshold value of supply amount (ratio) for making reactant gas reaction pattern, make to react
Property gas supply amount (ratio) be less than the metal mode of reaction pattern and set the supply amount (ratio) of reactant gas
Transition mode between reaction pattern and metal mode.It, can by reducing the ratio of reactant gas in metal mode
Attachment of the reactant gas to target material surface is reduced, film forming speed is accelerated.Moreover, in metal mode, due to reactive gas
The supply amount of body is few, so at least any one the concentration ratio being for example capable of forming in O concentration or N concentration has stoichiometric composition
The low film of film.That is, the containing ratio for being capable of forming Cr is relatively high, and O containing ratio, the lower film of N containing ratio.
As the condition for the metal mode for forming the first reflex inhibition layer 13, such as the flow of oxygen system gas can be set as
The flow of nitrogen system gas is set as 30~60sccm, the flow of rare gas is set as 60~150sccm by 5~45sccm.Separately
Outside, target, which applies power, can be set to 2.0~6.0kW, and the application voltage of target can be set to 360~460V.
As sputtering target material, as long as containing Cr, for example, in addition to chromium metal, also can be used chromium oxide, chromium nitride,
The chromium based material such as chrome hydroxide.As oxygen system gas, such as oxygen (O can be used2), carbon dioxide (CO2), oxides of nitrogen gas
(N2O、NO、NO2) etc..Wherein, because oxidability height is, it is preferable to use oxygen (O2) gas.In addition, nitrogen can be used as nitrogen system gas
(N2) etc..As rare gas, such as helium, neon, argon gas, Krypton and xenon can be used etc..In addition, except above-mentioned reactive gas
Other than body, hydrocarbon system gas can also be supplied, such as methane gas, butane gas can be used etc..
In the present embodiment, the flow of reactant gas and sputtering target material are applied into power setting at as metal mode
Condition, using containing Cr sputtering target material carry out reactive sputtering film process, pressed to be formed on transparent substrate 11
The first reflection suppression of the O, the N of 10~30 atom % of Cr, 15~45 atom % according to containing ratio respectively containing 25~75 atom %
Preparative layer 13.
In addition, the first reflex inhibition layer 13 is formed as composition in the case where uniform single film on film thickness direction,
Do not change the type of reactant gas, flow and formed a film, but occur on film thickness direction in O containing ratio, N containing ratio
Change and make to form in inclined situation, can suitably change oxygen in the type and/or flow, reactant gas of reactant gas
It is the ratio etc. of gas and/or nitrogen system gas.Alternatively, it is also possible to change configuration and/or the method for supplying gas of gas supply port
Deng.
(formation process of light shield layer)
Next, forming light shield layer 14 in the first reflex inhibition layer 13.The formation is formed a film by reactive sputtering,
Reactive sputtering uses the sputtering target material containing Cr and the sputter gas comprising nitrogen system gas and rare gas.At this moment, as at
Film condition, the flow that reactant gas contained by sputter gas may be selected become the flow of metal mode.
As target, as long as containing Cr, such as in addition to chromium metal, chromium oxide, chromium nitride, oxynitriding also can be used
The chromium based material such as chromium.As nitrogen system gas, nitrogen (N can be used2) etc..As rare gas, for example, can also be used helium, neon,
Argon gas, Krypton and xenon etc..In addition, oxygen system above-mentioned gas, hydrocarbon system gas can also be supplied in addition to above-mentioned reactant gas
Body.
In the present embodiment, the flow of reactant gas and sputtering target material are applied into power setting at as metal mode
Condition, reactive sputtering is carried out using the sputtering target material containing Cr, to be formed in the first reflex inhibition layer 13 according to containing
There are the light shield layer 14 of the N of Cr of the rate respectively containing 70~95 atom %, 5~30 atom %.
In addition, the membrance casting condition as light shield layer 14, such as the flow of nitrogen system gas can be set as 1~60sccm, it will
The flow of rare gas is set as 60~200sccm.Furthermore it is possible to target application power is set as 3.0~7.0kW, it can be by target
The application voltage of material is set as 370~380V.
(formation process of the second reflex inhibition layer)
Next, forming the second reflex inhibition layer 15 on light shield layer 14.The formation and the first reflex inhibition layer 13 are same,
The flow of reactant gas and target are applied into power setting into the condition for becoming metal mode, use the sputtering target containing Cr
Material carries out the film forming of reactive sputtering.It is formed as a result, according to containing ratio on light shield layer 14 respectively containing 30~75 atom %'s
The second reflex inhibition layer 15 of the N of Cr, the O of 20~50 atom %, 5~20 atom %.
As the condition for the metal mode for forming the second reflex inhibition layer 15, such as the flow of oxygen system gas can be set as 8
The flow of nitrogen system gas is set as 30~60sccm, the flow of rare gas is set as 60~150sccm by~45sccm.In addition,
Target can be applied into power and be set as 2.0~8.0kW, the application voltage of target can be set as 420~460V.
In addition, in the case where making the second reflex inhibition layer that there is the inclined situation of composition, as set forth above, it is possible to suitably change reaction
The property type of gas and/or the ratio etc. of oxygen system gas and/or nitrogen system gas in flow, reactant gas.
By the above-mentioned means, the photomask blank 1 of present embodiment can be obtained.
It should be noted that the film forming of each layer in photomask 12 can be used in-line arrangement sputtering equipment in a manner of in-situ
It carries out.In the case where non-in-line arrangement, need to make transparent substrate for except 11 withdrawing device of transparent substrate after the film forming of each layer
11 are exposed in an atmosphere, and surface oxidation or surface carbonation often occur for each layer.As a result, it is right to may result in photomask 12
It changes in the reflectivity or etch-rate of exposure light.In this respect, if it is in-line arrangement, then without taking transparent substrate 11
Out except device and each layer can be continuously formed by being exposed to the atmosphere, therefore, be able to suppress undesirable element to shading
Film 12 invades.
In addition, due to the first reflex inhibition layer 13, being hidden in the case where forming photomask 12 using in-line arrangement sputtering equipment
Photosphere 14, the second reflex inhibition layer 15 each layer between have and recur the inclined composition tilting zone (transition zone) of composition,
Therefore, can enable using photomask blank by etching (especially wet etching) formed shading film figure section it is smooth and
It is close vertical, therefore preferably.
The manufacturing method > of < photomask
Next, being illustrated to the method for using above-mentioned photomask blank 1 to manufacture photomask.
(formation process of etchant resist)
Firstly, being coated with resist in the second reflex inhibition layer 15 in the photomask 12 of photomask blank 1, it is dried
And form etchant resist.As resist, need to select resist appropriate according to used drawing apparatus, can be used positivity or
The resist of negativity.
(formation process of corrosion-resisting pattern)
Next, pattern as defined in being described on etchant resist using drawing apparatus.In general, being used in production display device manufacture
When photomask, laser description device is used.After description, by implementing development to etchant resist and cleaning, defined resist pattern is formed
Case.
In the present embodiment, due to reducing the reflectivity of the second reflex inhibition layer 15, describe on etchant resist
When pattern, the reflection for describing light (laser) can be reduced.It therewith can thereby, it is possible to form the high corrosion-resisting pattern of pattern accuracy
Form the high mask pattern of dimensional accuracy.
(formation process of mask pattern)
Next, etching photomask 12 and using corrosion-resisting pattern as mask, it is capable of forming mask pattern.Etching can be with
It is wet etching, is also possible to dry-etching.In general, in display device manufacture with carrying out wet etching in photomask, as
Etching solution used in wet etching (etchant), such as the chromium etching solution containing ammonium ceric nitrate and perchloric acid can be used.
In the present embodiment, due to the first reflex inhibition layer 13 on the thickness direction of photomask 12, light shield layer
14 and second the consistent mode of etch-rate of reflex inhibition layer 15 have adjusted the composition of each layer, therefore after wet etching capable of being made
Cross sectional shape close to vertical, i.e., the cross sectional shape of shading film figure (mask pattern) relative to transparent substrate 11 close to vertical,
Higher CD uniformity (CD Uniformity) can be obtained.
(stripping process)
Next, corrosion-resisting pattern is removed, obtain being formed with shading film figure (mask pattern) on transparent substrate 11
Photomask.
As above, the photomask of present embodiment can be obtained.
The manufacturing method > of < display device
Next, being illustrated to the method for using above-mentioned photomask to manufacture display device.
(preparatory process)
Firstly, the mask that the photomask as obtained from the manufacturing method of above-mentioned photomask is placed in exposure device is carried
On platform, relative to be formed on the substrate of display device etchant resist with ilm substrate against corrosion, by photomask across exposure device
Projection optical system (passing through projection exposure mode) it is opposed with the etchant resist being formed on substrate.
(exposure process (pattern transfer printing process))
Then, anti-aging drug process is executed, to photomask irradiation exposure light, on the substrate for being formed in display device
Etchant resist transfers pattern.
As exposure light, such as can be used in 365nm~436nm wave band single-wavelength light (i line (wavelength 365nm),
H line (wavelength 405nm), g line (wavelength 436nm) etc.) or light comprising multi-wavelength (for example, i line (wavelength 365nm), h line
(405nm), g line (wavelength 436nm)) complex light.The case where if it is large-scale photomask is used, exposes from the aspect of light quantity
Complex light can be used in light light.
In the present embodiment, the reflectivity and drop at the table back side of shading film figure (mask pattern) are reduced due to using
The photomask of the low reflection rate dependence of backside reflection rate manufactures display device (display panel), therefore can be shown
Uniform display device (display panel).
The effect > of < present embodiment
According to the present embodiment, it can be achieved that one or more effect below.
(a) photomask blank 1 of present embodiment passes through the first reflex inhibition layer 13 of stacking, light shield layer 14 and the second reflection
Inhibition layer 15 and form photomask 12, the reflectivity at the table back side in the range of being 365nm~436nm with exposure wavelength is
10% or less and the backside reflection rate in above-mentioned wave-length coverage wavelength dependency be 5% optical characteristics below.According to this
Photomask blank 1, can in the entire wave band that exposure wavelength is 365nm~436nm when as photomask irradiation exposure light
Inhibit the reflection of the light at surface and the back side, therefore can reduce the light summation of the reflected light at the table back side.Especially by backside reflection rate
Wavelength dependency be set as 5% hereinafter, can make backside reflection rate fifty-fifty in the whole region of above-mentioned wave-length coverage reduces, because
This is able to suppress the return light towards the photomask back side being unevenly affected to display.As a result, it is possible to inhibit using light
Display caused by the light reflection at the table back side by photomask when fabrication mask display device is uneven.
(b) preferably, in the whole region for the range that exposure wavelength is 365nm~436nm, the back of photomask blank 1
Face reflectivity is less than surface reflectivity.Thereby, it is possible to inhibit light reflection in broadband, total light of light reflection can be further decreased
Amount.
(c) preferably, using the surface reflectivity of photomask blank 1 and backside reflection rate as the longitudinal axis and using wavelength as
In the reflectance spectrum of horizontal axis, in the wave band that wavelength is 300nm~500nm, the reflectance spectrum of photomask blank 1 is downward
Convex curve, wavelength corresponding with minimum value (the bottom peak) of surface reflectivity and backside reflection rate are located at 350nm~450nm.
Thereby, it is possible to steadily manufacture more pieces with high yield to can inhibit the non-uniform photomask blank of display.
(d) preferably, in the range of exposure wavelength is 365nm~436nm, the backside reflection rate of photomask blank 1
The wavelength dependency of wavelength dependency specific surface reflectivity is small.That is, the variable quantity of backside reflection rate is excellent in above-mentioned wave-length coverage
Select the variable quantity of specific surface reflectivity small.Thereby, it is possible to further suppress the return light at the photomask back side, can further decrease
Display is uneven.
(e) preferably, in the wave-length coverage of 530nm or more, the above-mentioned surface reflectivity of photomask blank 1 be 10% with
On.Thereby, it is possible to improve the detection of the dimension measurement of the light-proofness film figure in the photomask produced using photomask blank 1
Precision.
(f) preferably, in photomask blank 1, the first reflex inhibition layer 13 is the chromium based material containing chromium, oxygen and nitrogen,
It is 25~75 atom %, O containing ratios with Cr containing ratio is the composition that 15~45 atom %, N containing ratios are 10~30 atom %,
Light shield layer 14 be the chromium based material containing chromium and nitrogen, have Cr containing ratio be 70~95 atom %, N containing ratios be 5~30 original
The composition of sub- %, the second reflex inhibition layer 15 are the chromium based material containing chromium, oxygen and nitrogen, and having Cr containing ratio is 30~75 former
Sub- %, O containing ratio is the composition that 20~50 atom %, N containing ratios are 5~20 atom %.By the way that each layer is set as above-mentioned composition,
The reflectivity that can reduce the table back side of photomask blank 1, easily can make them respectively become 10% or less.
(g) in addition, in the present embodiment, by will constitute the first reflex inhibition layer 13 of photomask 12, light shield layer 14,
Second reflex inhibition layer 15 is respectively set as compositing range shown in (f), reduces the O for reducing etch-rate and/or makes to etch
The concentration for the N that rate increases, is able to suppress the difference of the etch-rate of each layer, keeps the etch-rate of each layer consistent.Thereby, it is possible to make
Cross sectional shape (that is, cross sectional shape of mask pattern) when etched the photomask 12 of photomask blank 1 is relative to transparent substrate
11 close to vertically.Specifically, setting the side formed by etching and transparent substrate 11 in the cross sectional shape of mask pattern
Between angle be θ when, can make θ be located at 90 ° ± 30 ° in the range of.In addition, in addition to can make cross sectional shape close to it is vertical it
Outside, additionally it is possible to inhibit the etching residue or the first reflex inhibition layer 13 and the second reflex inhibition layer of the first reflex inhibition layer 13
15 missing (so-called undercutting) etc..As a result, it is possible to improve the CD uniformity of mask pattern (shading film figure), can be formed
100nm high-precision mask pattern below.
(h) in addition, in the present embodiment, photomask 12 pass through the first reflex inhibition layer 13 for making to constitute photomask 12,
Light shield layer 14, the etch-rate of each layer of the second reflex inhibition layer 15 are consistent, regardless of the length of etching period, etching solution it is deep or light,
How is the temperature of etching solution, can steadily ensure the up rightness of cross sectional shape.For example, in the optimal etch of photomask 12
Between (just etching time) be T when, even if etching period is set as 1.5 × T and carries out over etching, can also obtain
With up rightness identical when etching period is set as T.Specifically, shading film figure when etching period to be set as to T can be made
Section angulation θ 1 and the section angulation θ 2 when etching period being set as 1.5 × T and having carried out over etching
Difference become 10 ° or less.In addition similarly, the case where improving etchant concentration and the case where reducing etchant concentration
Under, it so that the difference of the section angulation of shading film figure is become 10 ° or less.In addition similarly, etching is being improved
The case where liquid temperature (for example, 42 DEG C) and in the case where reducing etching solution temperature (for example, 23 DEG C of room temperature), although etching solution temperature
Degree is higher to cause etch-rate higher, but the difference of the section angulation of shading film figure can be made to become 10 ° or less.
Here, the optimal etch time indicates along film thickness direction etching photomask 12 and until the surface of transparent substrate 11 starts exposing
Etching period.
(i) in photomask 12, the first reflex inhibition layer 13 and the second reflex inhibition layer 15 are the chromium containing chromium, oxygen and nitrogen
Based material, Cr of first reflex inhibition layer 13 preferably according to containing ratio respectively containing 50~75 atom %, 15~35 atom %
O, the N of 10~25 atom %, Cr of second reflex inhibition layer 15 preferably according to containing ratio respectively containing 50~75 atom %, 20~
The N of the O of 40 atom %, 5~20 atom %.
In the first reflex inhibition layer 13 and the second reflex inhibition layer 15, by further decreasing O containing ratio, it is able to suppress
The excessive descent of these layers etch-rate because caused by containing O.Therefore, can reduce for make constitute photomask 12 first
Reflex inhibition layer 13, light shield layer 14, each layer of the second reflex inhibition layer 15 the consistent purpose of etch-rate and be formulated to light shield layer
The containing ratio of carbon (C) in 14 makes light shield layer 14 become the non-carbon-containing layer without C.As a result, it is possible to improve in light shield layer 14
Cr containing ratio, optical concentration (OD) is maintained higher.
On the other hand, in the first reflex inhibition layer 13 and the second reflex inhibition layer 15, contained by further decreasing N
Rate is able to suppress the excessive increase of these layers etch-rate because caused by containing N.Therefore, can reduce for make constitute hide
First reflex inhibition layer 13 of light film 12, light shield layer 14, each layer of the second reflex inhibition layer 15 the consistent purpose of etch-rate and
The containing ratio for the N for containing light shield layer 14.As a result, it is possible to improve the Cr containing ratio of light shield layer 14, optical concentration (OD) is tieed up
Hold higher.
(j) preferably, the O containing ratio of the second reflex inhibition layer 15 is higher than the first reflex inhibition layer 13.Specifically, second
The O containing ratio of reflex inhibition layer 15 is preferably than the high 5 atom atom of %~10 % or more of the first reflex inhibition layer 13.In addition preferably
The N containing ratio on ground, the first reflex inhibition layer 13 is higher than the second reflex inhibition layer 15.Specifically, the N of the first reflex inhibition layer 13
Containing ratio is preferably than the high 5 atom atom of %~10 % or more of the second reflex inhibition layer 15.The research of people according to the present invention, first
In the case that reflex inhibition layer 13 and the second reflex inhibition layer 15 are formed by same material, whether identical regardless of forming, there are tables
The high tendency of the luminance factor back side of surface side.Therefore, further to the first reflex inhibition layer 13, the second reflex inhibition layer 15
The ratio of components (O containing ratio, N containing ratio) of each layer is found after being studied, by the way that the first reflex inhibition layer 13 and second is anti-
The ratio of components (O containing ratio, N containing ratio) for penetrating inhibition layer 15 is arranged to as above, the reflectivity of back side can be made to become and surface
The identical degree in side or specific surface side are lower.In this way, by the ratio of components (O containing ratio, N containing ratio) for changing each layer, it can
The reflectivity at the control table back side.
(k) preferably, the first reflex inhibition layer 13 and the second reflex inhibition layer 15 are respectively provided at least any in O and N
The region of composition variation occurs continuously or stepwise along film thickness direction for the containing ratio of kind element.By making the first reflex inhibition layer 13
And composition variation, the high area of the containing ratio that can either be locally introduced into O or N to each floor occur for each layer of the second reflex inhibition layer 15
Domain, and can the average containing ratio of the O of each layer or N be maintained lower.Thereby, it is possible to by the surface side of photomask blank 1 and
The reflectivity of back side maintains lower.
In addition, in the first reflex inhibition layer 13, the light shield layer 14, each layer of the second reflex inhibition layer 15 that constitute photomask 12
In, etch-rate decline can be made excessively by improving O containing ratio, etch-rate can be made to increase excessively alternatively, improving N containing ratio, but logical
The containing ratio for reducing O and/or N is crossed, the difference of the etch-rate of each layer because caused by containing these elements is able to suppress.That is, energy
Enough inhibit between the etch-rate of the first reflex inhibition layer 13 and the second reflex inhibition layer 15 and the etch-rate of light shield layer 14
Deviate from.As a result, it is possible to reduce for the first reflex inhibition layer 13, the reflection suppression of light shield layer 14, second for making composition photomask 12
The consistent purpose of etch-rate of each layer of preparative layer 15 and the N and/or carbon for containing light shield layer 14, or can make light shield layer 14 at
For carbon-free non-carbon-containing layer.As a result, it is possible to improve the Cr containing ratio in light shield layer 14, by optical concentration (OD) maintain compared with
It is high.
(l) preferably, there is the second reflex inhibition layer 15 O containing ratio to increase towards 14 side of light shield layer on film thickness direction
Region.As a result, in the second reflex inhibition layer 15, the O containing ratio with the interface portion of light shield layer 14 is locally improved, and make
Average O containing ratio on film thickness direction maintains low.As a result, it is possible in surface side (the second reflection suppression of photomask 12
15) layer obtains desired reflectivity, while being able to suppress the missing as caused by over etching on interface.
(m) preferably, there is the second reflex inhibition layer 15 N containing ratio to reduce towards 14 side of light shield layer on film thickness direction
Region.As a result, in the second reflex inhibition layer 15, not only the average N containing ratio on film thickness direction was maintained to a certain degree, but also
Locally reduce the N containing ratio with the interface portion of light shield layer 14.As a result, it is possible to inhibit the second reflex inhibition layer 15 and hide
The interface of photosphere 14 is lacked as caused by over etching.
(n) preferably, there is the first reflex inhibition layer 13 transparent substrate 11 of O containing ratio towards film thickness direction to increase and N
The containing ratio region reduced towards the transparent substrate 11 of film thickness direction.In the first reflex inhibition layer 13, by towards film thickness side
To transparent substrate 11 increase O containing ratio and make N containing ratio reduction, etch-rate can be made gradually to drop towards transparent substrate 11
It is low.Thereby, it is possible to inhibit the missing of the interface in the first reflex inhibition layer 13 and transparent substrate 11, mask artwork is further increased
The CD uniformity of case.
(o) in addition, according to the present embodiment, light shield layer 14, which preferably uses, contains chromium (Cr) and dichromium nitride (Cr2N key)
The chromium based material of conjunction state (chemical state).Light shield layer 14 by using contain Cr and Cr2The bond styles (chemical state) of N
Chromium based material, the excessive promotion of the etch-rate when N being able to suppress in light shield layer 14 containing specified amount, can make photomask
The cross sectional shape of pattern is close to vertically.
(p) in addition, according to the present embodiment, the first reflex inhibition layer 13 and the second reflex inhibition layer 15 preferably use and contain
One chromium nitride (CrN), chromium oxide (III) (Cr2O3) and chromium oxide (VI) (CrO3) bond styles (chemical state) chromium system material
Material.Contain Cr by the first reflex inhibition layer 13 and the second reflex inhibition layer 152O3、CrO3It, can be effectively etc. a variety of chromium oxide
Reduce the reflectivity at the table back side of photomask 12.In addition, since the first reflex inhibition layer 13 and the second reflex inhibition layer 15 contain
The chromium nitride of CrN is able to suppress the excessive descent of etch-rate caused by above-mentioned chromium oxide, so can make shading film figure
Cross sectional shape close to vertical.
(q) additionally preferably, according to the present embodiment, the first reflex inhibition layer 13 and the second reflex inhibition layer 15 are by making
It is carried out with the reactive sputtering of the sputtering target material containing Cr and the sputter gas comprising oxygen system gas, nitrogen system gas and rare gas
Film forming, light shield layer 14 by using the sputtering target material containing Cr and the sputter gas comprising nitrogen system gas and rare gas reaction
Property sputtering form a film, as the membrance casting condition of these reactive sputterings, select the stream of reactant gas contained by sputter gas
Amount becomes the flow of metal mode.It is easy that the first reflex inhibition layer 13, the light shield layer 14, second of photomask 12 will be constituted as a result,
Each layer of reflex inhibition layer 15 is adjusted into above-mentioned compositing range, in addition, the table back side of photomask 12 can either be effectively reduced
Reflectivity, but the cross sectional shape of shading film figure when can make 12 composition of photomask is close to vertical.
(r) preferably, it is formed a film in the first reflex inhibition layer 13 and each layer of the second reflex inhibition layer 15 by reactive sputtering
When, oxygen (O is used as oxygen system gas2Gas).If using O2Gas, since oxidability is stronger than other oxygen system gases, so even if
In the case where selecting metal mode to be formed a film, also more reliably each layer can be adjusted into above-mentioned compositing range.As a result,
Shading film figure when can either be effectively reduced the reflectivity at the table back side of photomask 12, and can make 12 composition of photomask
Cross sectional shape close to vertical.
(s) photomask blank 1 according to the present embodiment, since the reflectivity of surface side is low, on photomask 12
Etchant resist is set, by describing, when developing procedure formation corrosion-resisting pattern, can reduce and describe light in the anti-of 12 surface of photomask
It penetrates.Thereby, it is possible to improve the dimensional accuracy of corrosion-resisting pattern, the size of the shading film figure for the photomask being consequently formed can be improved
Precision.
(t) photomask manufactured by the photomask blank of present embodiment 1, since shading film figure is high-precision, and
The reflectivity at the table back side of shading film figure is reduced, so it is special to obtain high transfer when transferring pattern to transfer printing body
Property.
(u) in addition, in the present embodiment, as transparent substrate 11, use rectangle and bond length be 850mm with
Upper 1620mm substrate below, even if in the case where 1 enlargement of photomask blank, etching of the photomask 12 on film thickness direction
Rate is also able to maintain unanimously, can maintain higher by the CD uniformity for etching mask pattern obtained from photomask 12.
< other embodiments >
More than, an embodiment of the present invention is illustrated, but the present invention is not limited to the above embodiments, not
It is detached from the range of its design, can suitably change.
In the above-described embodiment, for photomask 12 are directly arranged on transparent substrate 11 the case where, is said
It is bright, however, the present invention is not limited thereto.For example, it can be the semi-transparent films by optical concentration lower than photomask 12 to be set to transparent base
Photomask blank between plate 11 and photomask 12.Preferably, semi-transparent film and photomask 12 are formed on transparent substrate 11
The photomask blank, also exposure wavelength be 365nm~436nm in the range of, make semi-transparent film for above-mentioned exposure light
Backside reflection rate be 10% hereinafter, the surface reflectivity of photomask is 10% hereinafter, also, above-mentioned in above-mentioned wave-length coverage
The wavelength dependency of the backside reflection rate of semi-transparent film is 5% or less.The photomask blank can be used as gray mask or gray scale
The photomask blank of mask comes using and gray mask or gray scale mask have used light when cutting down display device manufacture
The effect of mask count.Mask pattern in the gray mask or gray scale mask is semi-transparent film figure and/or photomask
Pattern.
Alternatively, it is also possible to replace semi-transparent film, transparent base is set to using by the phase shift film for making the phase shift of transmitted light
Photomask blank between plate 11 and photomask 12.Preferably, the institute of phase shift film and photomask 12 is formed on transparent substrate 11
Photomask blank is stated, also in the range of exposure wavelength is 365nm~436nm, makes phase shift film for the back side of above-mentioned exposure light
Reflectivity is 10% hereinafter, the surface reflectivity of photomask is 10% hereinafter, also, above-mentioned semi-transparent in above-mentioned wave-length coverage
The wavelength dependency of the backside reflection rate of film is 5% or less.The photomask blank can be used for phase shifting mask, the phase shifting mask tool
There is the high pattern resolution effect using phase shift effect.Mask pattern in the phase shifting mask is phase shift film figure or phase
Move film figure and shading film figure.
The material for constituting photomask 12 is chromium based material, and above-mentioned semi-transparent film and phase shift film are preferably used compared to the chromium
Based material has the material of etching selectivity.As this material, it can be used and contain molybdenum (Mo), zirconium (Zr), titanium (Ti), tantalum (Ta)
With the metal silicide based material of silicon (Si), it is also suitable for using further containing at least any one in aerobic, nitrogen, carbon or fluorine
Material.For example, being suitble to using metal silicides, the oxide of metal silicide, metal silication such as MoSi, ZrSi, TiSi, TaSi
The nitride of object, the oxynitride of metal silicide, the carbonitride of metal silicide, the oxycarbide of metal silicide, gold
Belong to the carbon oxynitride of silicide.In addition, these semi-transparent films and/or phase shift film be also possible to it is upper by being enumerated as functional membrane
State the stacked film of film composition.
In addition, being each 1 layer to the first reflex inhibition layer 13 and the second reflex inhibition layer 15 in the above-described embodiment
The case where be illustrated, however, the present invention is not limited thereto.For example, it is also possible to which each layer to be set as to 2 layers or more of multilayer.
In addition, in the above-described embodiment, can also be formed on photomask 12 by having erosion compared with photomask 12
Carve the etching mask film that the material of selectivity is constituted.
In addition, in the above-described embodiment, can also be formed between transparent substrate 11 and photomask 12 by with shading
Film compares the etching barrier film that the material with etching selectivity is constituted.Above-mentioned etching mask film, etching barrier film by compared to
There is the material, that is, chromium based material for constituting photomask 12 material of etching selectivity to constitute.As this material, can enumerate containing
Molybdenum (Mo), zirconium (Zr), titanium (Ti), tantalum (Ta) and silicon (Si) metal silicide based material or Si, SiO, SiO2、SiON、Si3N4
Etc. silicon systems material.
[embodiment]
Then, based on embodiment, further the present invention is described in detail, but the present invention is not limited to these Examples.
1 > of < embodiment
In the present embodiment, using in-line arrangement sputtering equipment, by sequence described in above embodiment, in such as Fig. 1 institute
The first reflex inhibition layer, light shield layer and the second reflection suppression are laminated on the transparent substrate that the substrate size shown is 1220mm × 1400mm
Preparative layer produces the photomask blank for having photomask.
The membrance casting condition of first reflex inhibition layer are as follows: sputtering target material is Cr sputtering target material, and the flow of reactant gas is distinguished
Oxygen (O is selected in the range of 5~45sccm2) gas flow, in the range of 30~60sccm select nitrogen (N2) gas flow,
The flow that argon (Ar) gas is selected in the range of 60~150sccm, thus becomes metal mode, also, 2.0~6.0kW's
Setting target applies power in range, and target is set in the range of 420~430V and applies voltage.In addition, the first reflection suppression
Substrate conveying speed when layer film forming is 350mm/min.
The membrance casting condition of light shield layer are as follows: sputtering target material is Cr sputtering target material, the flow of reactant gas respectively from 1~
Nitrogen (N is selected in the range of 60sccm2) gas flow, in the range of 60~200sccm select argon (Ar) gas flow, thus
As metal mode, also, target is set in the range of 3.0~7.0kW and applies power, set in the range of 370~380V
Targeting material applies voltage.In addition, the substrate conveying speed when film forming of light shield layer is 200mm/min.
The membrance casting condition of second reflex inhibition layer are as follows: sputtering target material is Cr sputtering target material, and the flow of reactant gas is distinguished
Oxygen (O is selected in the range of 8~45sccm2) gas flow, in the range of 30~60sccm select nitrogen (N2) gas flow,
The flow of argon (Ar) gas is selected in the range of 60~150sccm, to become metal mode, also, 2.0~6.0kW's
Setting target applies power in range, and target is set in the range of 420~430V and applies voltage.In addition, the second reflection suppression
The substrate conveying speed when film forming of layer is 300mm/min.
Film thickness direction is determined to the photomask of obtained photomask blank by X-ray photoelectron spectroscopy (XPS)
Composition, can confirm that each layer in photomask is distributed with composition shown in Fig. 2.Fig. 2 is the photomask blank for indicating embodiment 1
The figure of composition analysis result on film thickness direction, what horizontal axis indicated is sputtering time, and what the longitudinal axis indicated is the content [original of element
Sub- %].Sputtering time indicates the depth away from shading film surface.
In Fig. 2, the region of about 5min is surface natural oxidizing layer from surface to depth, about from depth about 5min to depth
The region of 16min is the second reflex inhibition layer, is transition zone from depth about 16min to the region of depth about 40min, about from depth
40min is light shield layer to the region of depth about 97min, is transition zone from depth about 97min to the region of depth about 124min, from
Depth about 124min is the first reflex inhibition layer to the region of depth about 132min, and the region from depth about 132min is transparent
Substrate.
Here, the film thickness of the photomask determined by film thickness gauge is 198nm, above-mentioned surface natural oxidizing layer, the second reflection
Inhibition layer, transition zone, light shield layer, transition zone, the first reflex inhibition layer each film thickness be respectively: surface natural oxidizing layer is about
4nm, the second reflex inhibition layer are about 21nm, transition zone is about 35nm, light shield layer is about 88nm, transition zone is about 39nm, first
Reflex inhibition layer is about 11nm.
As shown in Fig. 2, the first reflex inhibition layer be CrON film, the Cr containing 55.4 atom %, 20.8 atom % N,
The O of 23.8 atom %.The containing ratio of these elements is that N in the first reflex inhibition layer becomes the part at peak (sputtering time is
The region of 123min) value that determines.There is first reflex inhibition layer inclination as shown in Figure 2 to form, and have in film thickness direction
On increase towards transparent substrate O containing ratio and N containing ratio reduce part.In addition, each element exists in the first reflex inhibition layer
Average containing ratio on film thickness direction are as follows: it be 18 atom %, O is 25 atom % that Cr, which is 57 atom %, N,.
Light shield layer is CrN film, the N of the Cr containing 92.0 atom %, 8.0 atom %.The containing ratio of these elements is to hide
The value that central part (region that sputtering time is 69min) on the film thickness direction of photosphere determines.In addition, in light shield layer,
It is 91 atom %, N is 9 atom % that average containing ratio of each element on film thickness direction, which is Cr,.
Second reflex inhibition layer is CrON film, the Cr containing 50.7 atom %, the N of 12.2 atom %, 37.1 atom %
O.The containing ratio of these elements is central part (the sputtering time 16min in the region that the O in the second reflex inhibition layer increases
Region) value that determines.There is second reflex inhibition layer inclination as shown in Figure 2 to form, and have the direction on film thickness direction
The part that light shield layer side O containing ratio increases and N containing ratio reduces.Here, each element is in film thickness side in the second reflex inhibition layer
Upward average containing ratio are as follows: it be 17 atom %, O is 31 atom % that Cr, which is 52 atom %, N,.In addition, in the second reflex inhibition layer
Surface, surface natural oxidizing layer is formed with because being exposed to the atmosphere, it is believed that the layer is detected because aoxidizing or being carbonized
Higher O containing ratio and C containing ratio.
In addition, XPS measurement result is based on, to the first reflex inhibition layer, light shield layer, the second reflection suppression for constituting photomask
The bond styles (chemical state) of each layer of layer have carried out spectrum analysis.As a result, the first reflex inhibition layer and the second reflection suppression
Preparative layer contains a chromium nitride (CrN), chromium oxide (III) (Cr2O3), chromium oxide (VI) (CrO3), it is the chromium containing chromium, oxygen and nitrogen
Based material (chromium compound).In addition, light shield layer contains chromium (Cr) and dichromium nitride (Cr2It N), is the chromium based material containing chromium and nitrogen
(chromium compound).
(evaluation of photomask blank)
By the following method, to the optical concentration of the photomask of the photomask blank of embodiment 1, the table back side of photomask
Reflectivity is evaluated.
For the photomask blank of embodiment 1, spectrophotometer (society, Shimadzu Scisakusho Ltd system is utilized
" SolidSpec-3700 ") optical concentration of photomask is determined, in the g line (wavelength of the wave band as exposure light
436nm) place is 5.0.In addition, using spectrophotometer (Shimadzu Scisakusho Ltd's system " SolidSpec-3700 ") to screening
The reflectivity at the table back side of light film is determined.Specifically, determining the second of photomask respectively using spectrophotometer
The reflectivity (backside reflection rate) of the transparent substrate side of the reflectivity (surface reflectivity) and photomask of reflex inhibition layer side.It is tied
Fruit is to have obtained reflectance spectrum as shown in Figure 3.Fig. 3 indicates the reflectivity light at the table back side of the photomask blank of embodiment 1
Spectrum, that horizontal axis indicates is wavelength [nm], and that the longitudinal axis indicates is reflectivity [%].
As shown in figure 3, it will be acknowledged that the bottom peak of the reflectance spectrum at the table back side of the photomask blank of embodiment 1
Wavelength is located near 436nm, in addition, reflectivity can be greatly reduced for the light of wide wave-length coverage.Specifically, in wavelength
In 365nm~436nm, the surface reflectivity of photomask is 10.0% or less (7.7% (wavelength 365nm), 1.8% (wavelength
405nm), 1.1% (wavelength 413nm), 0.3% (wavelength 436nm)), the backside reflection rate of photomask is 7.5% or less (6.2%
(wavelength 365nm), 4.7% (wavelength 405nm), 4.8% (wavelength 436nm)).It can confirm, the energy in wavelength 365nm~436nm
It is enough that the reflectivity at the table back side of photomask is reduced to 10% hereinafter, reflectivity especially to the light of wavelength 436nm, can make
Surface reflectivity reaches 0.3%, and backside reflection rate is made to reach 4.8%.
In addition, the dependence of the surface reflectivity of photomask in the range of exposure wavelength is 365nm~436nm is
7.4%, the dependence of backside reflection rate is 1.6%.
In addition, the surface reflectivity of the photomask at wavelength 530nm is 11.8%.
Minimum value (bottom peak) phase in the wave band that wavelength is 300nm~500nm, with surface reflectivity and backside reflection rate
Corresponding wavelength (bottom spike is long) is；Surface reflectivity is 436nm, and backside reflection rate is 415.5nm.
(evaluation of shading film figure)
Shading film figure is formed on the transparent substrate using the photomask blank of embodiment 1.Specifically, in transparent substrate
On photomask on form the positive resist film of phenolic aldehyde system after, carry out laser description (wavelength 413nm), development treatment and shape
At corrosion-resisting pattern.Later, using corrosion-resisting pattern as mask, wet etching is carried out by chromium etching solution, is formed on the transparent substrate
Shading film figure.The evaluation of shading film figure passes through the line and intermittent pattern (line and space of 1.9 μm of formation
Pattern), the cross sectional shape of shading film figure is observed using scanning electron microscope (SEM) to implement.Its result
It is, as shown in Figure 4, it is thus identified that cross sectional shape is close to vertically.Fig. 4 is being lost by wet type for the photomask blank to embodiment 1
The figure that the up rightness of the cross sectional shape for the shading film figure realized is illustrated is carved, what is respectively indicated is with the optimal etch time
(JET) section shape when etching period is set as 110%, 130%, 150% and has carried out over etching by (100%) on the basis of
Shape.In Fig. 4, it is laminated with shading film figure and film figure against corrosion on the transparent substrate, it is thus identified that the side of shading film figure exists
When JET100% and transparent substrate angulation is 70 °.Even if by etching period be set as JET 110%, 130% and
When 150%, the formed angle is also in the range of 60 °~80 °, can be by photomask figure regardless of etching period
It is vertical that the cross sectional shape of case, which is stably formed,.
As described above for example 1, about the photomask of photomask blank, by stacking gradually from transparent substrate side
One reflex inhibition layer, light shield layer and the second reflex inhibition layer, and make each layer that there is defined composition, it can be in wide wave-length coverage
The cross sectional shape of shading film figure when reducing the reflectivity at the table back side, and can make through wet etching composition, which becomes, to hang down
Directly.
(production of photomask)
Then, photomask is made using the photomask blank of embodiment 1.
Firstly, forming the positive corrosion-resisting agent of phenolic aldehyde system on the photomask of photomask blank.Then, it is filled using laser description
The pattern for describing TFT panel circuit pattern on the etchant resist is set, and then developed, rinsed, is consequently formed defined anti-
Corrosion figure case (minimum feature of foregoing circuit pattern is 0.75 μm).
Then, using corrosion-resisting pattern as mask, photomask composition is finally utilized by wet etching using chromium etching solution
Anticorrosive additive stripping liquid controlling removes corrosion-resisting pattern, and the light for being formed with shading film figure (mask pattern) on the transparent substrate is covered
Mould.For the photomask, the aperture opening ratio for the shading film figure (mask pattern) being formed on transparent substrate is (that is, be not formed
The transparent substrate of shading film figure accounts for the exposure ratio for being formed with the entire surface region of the photomask of shading film figure) it is 45%.
It is uniform using CD of the Seiko electronics nanosecond science and technology Co. Ltd. system " SIR8000 " to the shading film figure of the photomask
Property is determined.The measurement of CD uniformity, to the region of 1100mm × 1300mm in addition to the peripheral edge margin of substrate, 11
× 11 place is determined.
As a result, CD uniformity is 100nm, the CD of obtained photomask has good uniformity.
(production of LCD panel)
The photomask produced by embodiment 1 is placed on the mask carrying stage of exposure device, in display device
(TFT) pattern exposure is carried out with the transfer printing body for being formed with etchant resist on substrate, produces tft array.As exposure light, use
The complex light of the g line of i line comprising wavelength 365nm, the h line of wavelength 405nm and wavelength 436nm.
Produced tft array and colored filter, polarizing film, backlight are combined, TFT- is produced
LCD panel.As a result, having obtained the uniform TFT-LCD panel of display.It is thought that due to carrying out figure using photomask
When case exposes, it is able to suppress the light reflection at the table back side, and can reduce the reason of the light summation of reflected light.
(embodiment 2)
The present embodiment is by the membrance casting condition of the first reflex inhibition layer of embodiment 1, the membrance casting condition of the second reflex inhibition layer
It is changed to following conditions, the first reflex inhibition layer is laminated on the transparent substrate that substrate size is 1220mm × 1400mm, hides
Photosphere and the second reflex inhibition layer, have produced the photomask blank for having photomask.
The membrance casting condition of first reflection suppression film are as follows: sputtering target material is Cr sputtering target material, and the flow of reactant gas is distinguished
Oxygen (O is selected in the range of 25~45sccm2) gas flow, in the range of 40~60sccm select nitrogen (N2) gas flow,
The flow that argon (Ar) gas is selected in the range of 80~120sccm, thus becomes metal mode, also, 1.5~5.0kW's
Setting target applies power in range, and target is set in the range of 380~400V and applies voltage.In addition, the first reflection suppression
Substrate conveying speed when layer film forming is 300mm/min.
In addition, the membrance casting condition of the second reflection suppression film are as follows: sputtering target material is Cr sputtering target material, the flow of reactant gas
Oxygen (O is selected in the range of 8~25sccm respectively2) gas flow, in the range of 30~40sccm select nitrogen (N2) gas stream
Amount selects the flow of argon (Ar) gas in the range of 90~120sccm, thus becomes metal mode, also, in 3.5~8.0kW
In the range of setting target apply power, in the range of 435~455V set target apply voltage.In addition, the second reflection suppression
Substrate conveying speed when preparative layer forms a film is 250mm/min.
(evaluation of photomask blank)
For the photomask blank of embodiment 2, similarly to Example 1 to the table of the optical concentration of photomask, photomask
The reflectivity at the back side is evaluated.
G line (wavelength of the optical concentration of the photomask of the photomask blank of embodiment 2 in the wave band for being located at exposure light
436nm) place is 5.1.In addition it confirms, can make the bottom spike of the reflectance spectrum at the table back side is long to be located near 400nm, separately
Outside, reflectivity can be greatly reduced for the light in wide wave-length coverage.Specifically, in wavelength 365nm~436nm, shading
The surface reflectivity of film be 7.5% or less (7.5% (wavelength 365nm), 4.9% (wavelength 405nm), 4.9% (wavelength 413nm),
6.3% (wavelength 436nm)), the backside reflection rate of photomask is 5% or less (2.8% (wavelength 365nm), 1.6% (wavelength
405nm), 3.9% (wavelength 436nm)).Confirmation can be in wavelength 365nm~436nm by the reflectivity at the table back side of photomask
Be reduced to 7.5% hereinafter, the light especially for wavelength 405nm reflectivity, can make surface reflectivity become 4.9%, and
Backside reflection rate is set to become 1.6%.
In addition, the dependence of the surface reflectivity of photomask in the range of exposure wavelength is 365nm~436nm is
2.6%, the dependence of backside reflection rate is 2.5%.
In addition, the surface reflectivity of the photomask at wavelength 530nm is 22.8%.
It is opposite with the minimum value (bottom peak) of surface reflectivity and backside reflection rate in the wave band that wavelength is 200nm~500nm
The wavelength answered (bottom spike is long) are as follows: surface reflectivity 404nm, backside reflection rate are 394nm.
(production of photomask)
Then, photomask has been produced using the photomask blank of embodiment 2 similarly to Example 1, CD uniformity is
The CD of 92nm, obtained photomask have good uniformity.
(production of LCD panel)
The photomask produced by embodiment 2 is placed on the mask carrying stage of exposure device, in display device
(TFT) pattern exposure is carried out with the transfer printing body for being formed with etchant resist on substrate, produces tft array.As exposure light, use
The complex light of the g line of i line comprising wavelength 365nm, the h line of wavelength 405nm and wavelength 436nm.By produced TFT
Array and colored filter, polarizing film, backlight are combined, and TFT-LCD panel is produced.As a result, being shown
Show uniform TFT-LCD panel.It is thought that being able to suppress the table back side due to when carrying out pattern exposure using photomask
Light reflection, and can reduce the reason of the light summation of reflected light.
(embodiment 3)
The present embodiment uses the photomask blank of embodiment 1, and producing the line width with shading film figure is 1.2 μm narrow
The photomask of gap-like pattern produces photomask in addition to this similarly to Example 1.In addition, in produced photomask
In, the aperture opening ratio for being formed in the shading film figure on transparent substrate is 38%.
The CD uniformity of the shading film figure of the photomask is 82nm, and the CD of obtained photomask has good uniformity.
The photomask produced by embodiment 3 is placed on the mask carrying stage of exposure device, at display device (TFT)
Pattern exposure is carried out with the transfer printing body for being formed with etchant resist on substrate, produces tft array.As exposure light, packet is used
The complex light of the g line of the i line of the 365nm containing wavelength, the h line of wavelength 405nm and wavelength 436nm.By produced tft array,
Colored filter, polarizing film, backlight are combined, and TFT-LCD panel is produced.As a result, it is uniform to have obtained display
TFT-LCD panel.It is thought that it is able to suppress the light reflection at the table back side due to when carrying out pattern exposure using photomask,
And it can reduce the reason of the light summation of reflected light.
(embodiment 4)
The present embodiment is formed with phase shift film in the photomask blank of embodiment 1 between transparent substrate and photomask, removes
Except this, photomask blank is produced similarly to Example 1.
Phase shift film forms a film in the following manner.
The membrance casting condition of phase shift film are as follows: sputtering target material is MoSi sputtering target material (Mo:Si=1:4), by utilizing argon gas, nitrogen
Gas (N2), the reactive sputtering of the mixed gas of nitric oxide gas (NO), foring film thickness is being made of MoSiON for 183nm
Phase shift film.In addition, the gas flow of mixed gas are as follows: Ar gas is 40sccm, N2Gas is that 34sccm, NO gas are 34.5sccm.
In addition, the transmitance of the phase shift film is 27% (wavelength 405nm), phase difference is 173 ° (wavelength 405nm).
Then, similarly to Example 1, formed on phase shift film by the first reflex inhibition layer, light shield layer and the second reflection
The photomask that inhibition layer is constituted, produces photomask blank.
(evaluation of photomask blank)
The backside reflection rate of phase shift film in the photomask blank of embodiment 4 is 10.0% or less (4.2% (wavelength
365nm), 6.2% (wavelength 405nm), 9.2% (wavelength 436nm)).In addition, the surface reflectivity of photomask is 10.0% or less
(7.7% (wavelength 365nm), 1.8% (wavelength 405nm), 1.1% (wavelength 413nm), 0.3% (wavelength 436nm)).Embodiment 4
Photomask blank, in wavelength 365nm~436nm the backside reflection rate of phase shift film can be reduced to 10% hereinafter, and making
The surface reflectivity of photomask is reduced to 10% hereinafter, in turn, make the wavelength dependency 5% of the backside reflection rate of phase shift film with
Under.
(production of photomask and the production of LCD panel)
Then, photomask is produced using the photomask blank of embodiment 4.
Firstly, forming the positive corrosion-resisting agent of phenolic aldehyde system on the photomask of photomask blank.Then, it is filled using laser description
It sets, describes aperture on the etchant resist and be 1.2 μm of poroid pattern, and then developed, cleaned, the first resist pattern is consequently formed
Case.
Later, using the first corrosion-resisting pattern as mask, using chromium etching solution by wet etching by photomask composition, in phase
It moves and forms shading film figure on film.
Then, using shading film figure as mask, pass through wet etching for phase shift film composition, shape using silication molybdenum etching liquid
At phase shift film figure.Later, the first corrosion-resisting pattern is removed.
Then, etchant resist is formed in a manner of covering shading film figure, utilizes laser description device depicting pattern, Jin Erjin
Row development is cleaned, and the second corrosion-resisting pattern for being used to form photo-shield strip is thus formed on phase shift film figure.
Then, using the second corrosion-resisting pattern as mask, using chromium etching solution by wet etching by photomask composition, in phase
It moves and forms photo-shield strip shading film figure on film, finally, the second film figure against corrosion is removed, produce photomask.
In this way, obtained being formed on the transparent substrate phase shift film figure that aperture is 1.2 μm and by phase shift film figure with
The photomask for the photo-shield strip that the lit-par-lit structure of shading film figure is constituted.
The CD uniformity of the phase shift film figure of the photomask is 90nm, and the CD of obtained photomask has good uniformity.
In addition, producing TFT-CLD panel using the photomask produced by embodiment 4, it is equal display has as a result been obtained
Even TFT-LCD panel.It is thought that the light for being able to suppress the table back side is anti-due to when carrying out pattern exposure using photomask
It penetrates, and can reduce the reason of the light summation of reflected light.
(comparative example 1)
As comparative example, be laminated on the transparent substrate that substrate size is 1220mm × 1400mm the first reflex inhibition layer,
Light shield layer and the second reflex inhibition layer, produce the photomask blank for having photomask.
The membrance casting condition of first reflex inhibition layer are as follows: sputtering target material is Cr sputtering target material, and the flow of reactant gas is distinguished
Carbon dioxide gas (CO is selected in the range of 100~250sccm2) flow, selected in the range of 150~350sccm
Nitrogen (N2) gas flow, in the range of 0~15 select methane (CH4) gas flow, selected in the range of 150~300sccm
The flow of argon (Ar) gas is selected, to become reaction pattern, also, target is set in the range of 2.0~7.0kW and applies power.
Here, substrate conveying speed when the first reflex inhibition layer forms a film is 200mm/min, formed a film three times.
The membrance casting condition of light shield layer are as follows: sputtering target material is Cr sputtering target material, the flow of reactant gas respectively from 1~
Nitrogen (N is selected in the range of 60sccm2) gas flow, in the range of 60~200sccm select argon (Ar) gas flow, thus
As metal mode, also, target is set in the range of 5.0~8.0kW and applies power.In addition, base when light shield layer forms a film
Plate conveying speed is 200mm/min.
The membrance casting condition of second reflex inhibition layer are as follows: sputtering target material is Cr sputtering target material, and the flow of reactant gas is distinguished
Carbon dioxide gas (CO is selected in the range of 100~300sccm2) flow, selected in the range of 150~350sccm
Nitrogen (N2) gas flow, in the range of 0~15sccm select methane (CH4) gas flow, from the range of 150~300sccm
The flow of interior selection argon (Ar) gas to become reaction pattern, also, sets target in the range of 2.0~7.0kW and applies function
Rate.In addition, substrate conveying speed when the second reflex inhibition layer forms a film is 200mm/min, formed a film three times.
In the same manner as the above embodiments 1, the optical concentration of photomask is determined to the photomask blank of comparative example 1, is hidden
The reflectivity at the table back side of light film.As a result, g line (wavelength of the optical concentration of photomask in the wave band for being located at exposure light
436nm) place is 5.1.In addition, the surface reflectivity of photomask is 5.0% or less (2.8% in wavelength 365nm~436nm
(wavelength 365nm), 3.5% (wavelength 405nm), 3.9% (wavelength 413nm), 4.8% (wavelength 436nm)), the back side of photomask
Reflectivity is 12% or less (11.2% (wavelength 365nm), 7.1% (wavelength 405nm), 4.9% (wavelength 436nm)).In wavelength
In 365nm~436nm, although the surface reflectivity of photomask is 5% hereinafter, backside reflection rate has been more than 10%, in wave
It is 11.2% at long 365nm.
In addition, the surface reflection rate dependence of photomask in the range of exposure wavelength is 365nm~436nm is
2.0%, backside reflection rate dependence is 6.3%.
Minimum value (bottom peak) phase in the wave band that wavelength is 300nm~500nm, with surface reflectivity and backside reflection rate
Corresponding wavelength (bottom spike is long) are as follows: surface reflectivity 337nm, backside reflection rate are 474nm.
(production of photomask)
Then, using the photomask blank of comparative example 1, photomask is produced similarly to Example 1.It measures obtained
The CD uniformity of the shading film figure of photomask the result is that 155nm, poorer than embodiment 1,2.
(production of LCD panel)
The photomask produced by comparing example 1 is placed on the mask carrying stage of exposure device, in display device
(TFT) pattern exposure is carried out with the transfer printing body for being formed with etchant resist on substrate, produces tft array.As exposure light, use
The complex light of the g line of the h line and wavelength 436nm of i line, wavelength 405nm comprising wavelength 365nm.By produced TFT battle array
Column, colored filter, polarizing film, backlight are combined, and TFT-LCD panel is produced.As a result, using comparative example 1
In the TFT-LCD panel that photomask is produced, it is uneven that confirmation produces display.It is thought that due to being covered in the light of comparative example 1
In mould, the light reflection that could not be adequately suppressed when carrying out pattern exposure in exposure wavelength 365nm~436nm, especially shading
The light of back of the membrane reflects, the reason for as a result causing the light summation of reflected light to increase.
Claims (16)
1. a kind of photomask blank, used when making display device manufacture photomask comprising:
Transparent substrate, by being constituted for the exposure substantially transparent material of light；
Photomask is set on the transparent substrate, by being constituted for the substantially opaque material of the exposure light,
The photomask has the first reflex inhibition layer, light shield layer, the second reflex inhibition layer from the transparent substrate side,
Using the face of the photomask side in the two sides of the photomask blank as surface, by the face of the transparent substrate side
Surface reflectivity and the back side when as the back side, in the range of exposure wavelength is 365nm~436nm, for the exposure light
Reflectivity be respectively 10% hereinafter, and the backside reflection rate in the wave-length coverage wavelength dependency be 5% or less.
2. photomask blank as described in claim 1, which is characterized in that
Whole region in the range of exposure wavelength is 365nm~436nm, the backside reflection rate is than the surface reflectivity
It is small.
3. photomask blank as claimed in claim 1 or 2, which is characterized in that
Using the surface reflectivity of the photomask blank and the backside reflection rate as the longitudinal axis and using wavelength as cross
In the reflectance spectrum of axis, in the wave band that wavelength is 300nm~500nm, the reflectivity at the surface and the back side
Spectrum is downwardly convex curve respectively, corresponding with the minimum value of the surface reflectivity and the backside reflection rate, that is, bottom peak
Wavelength is located at 350nm~450nm.
4. photomask blank as claimed in claim 1 or 2, which is characterized in that
In the range of exposure wavelength is 365nm~436nm, the wavelength dependency of the backside reflection rate is than the surface reflection
The wavelength dependency of rate is small.
5. photomask blank as claimed in claim 1 or 2, which is characterized in that
In the wave-length coverage of 530nm or more, the surface reflectivity is 10% or more.
6. photomask blank as claimed in claim 1 or 2, which is characterized in that
First reflex inhibition layer be the chromium based material containing chromium, oxygen and nitrogen, with chromium containing ratio be 25~75 atom %,
The composition that the containing ratio of oxygen is 15~45 atom %, the containing ratio of nitrogen is 10~30 atom %,
The light shield layer is the chromium based material containing chromium and nitrogen, and the containing ratio with chromium is the containing ratio of 70~95 atom %, nitrogen
For the composition of 5~30 atom %,
Second reflex inhibition layer be the chromium based material containing chromium, oxygen and nitrogen, with chromium containing ratio be 30~75 atom %,
The composition that the containing ratio of oxygen is 20~50 atom %, the containing ratio of nitrogen is 5~20 atom %.
7. photomask blank as claimed in claim 6, which is characterized in that
In first reflex inhibition layer, the containing ratio of chromium is 50~75 atom %, and the containing ratio of oxygen is 15~35 atom %,
The containing ratio of nitrogen is 10~25 atom %,
In second reflex inhibition layer, the containing ratio of chromium is 50~75 atom %, and the containing ratio of oxygen is 20~40 atom %,
The containing ratio of nitrogen is 5~20 atom %.
8. photomask blank as claimed in claim 6, which is characterized in that
The containing ratio of the oxygen of second reflex inhibition layer is higher than first reflex inhibition layer.
9. photomask blank as claimed in claim 6, which is characterized in that
The containing ratio of the nitrogen of first reflex inhibition layer is higher than second reflex inhibition layer.
10. photomask blank as claimed in claim 1 or 2, which is characterized in that
The transparent substrate is rectangular substrate, and the bond length of the substrate is 850mm or more 1620mm or less.
11. photomask blank as claimed in claim 1 or 2, which is characterized in that
Semi-transparent film is also equipped between the transparent substrate and the photomask, the semi-transparent film has than the photomask
The low optical concentration of optical concentration.
12. photomask blank as claimed in claim 1 or 2, which is characterized in that
The phase shift film for making the phase shift of transmitted light is also equipped between the transparent substrate and the photomask.
13. a kind of manufacturing method of photomask, which is characterized in that comprise the following steps:
Prepare the photomask blank according to any one of claims 1 to 10；
Etchant resist is formed on the photomask, using the corrosion-resisting pattern that is formed by the etchant resist as mask to the photomask
It is etched, forms shading film figure on the transparent substrate.
14. a kind of manufacturing method of photomask, which is characterized in that comprise the following steps:
Prepare the photomask blank described in claim 11；
Etchant resist is formed on the photomask, using the corrosion-resisting pattern that is formed by the etchant resist as mask to the photomask
It is etched, forms shading film figure on the transparent substrate；
The semi-transparent film is etched using the shading film figure as mask, is formed on the transparent substrate semi-transparent
Film figure.
15. a kind of manufacturing method of photomask, which is characterized in that comprise the following steps:
Prepare the photomask blank described in claim 12；
Etchant resist is formed on the photomask, using the corrosion-resisting pattern that is formed by the etchant resist as mask to the photomask
It is etched, forms shading film figure on the transparent substrate；
The phase shift film is etched using the shading film figure as mask, forms phase shift film figure on the transparent substrate
Case.
16. a kind of manufacturing method of display device, which is characterized in that
With exposure process, in the exposure process, by the system of the photomask as described in any one of claim 13~15
The photomask that the method for making obtains is positioned on the mask carrying stage of exposure device, will be formed in the photomask on the photomask
Pattern, the semi-transparent film figure, at least one mask pattern exposure in the phase shift film figure are transferred in and are formed in display
On resist on device substrate.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017-249645 | 2017-12-26 | ||
| JP2017249645 | 2017-12-26 | ||
| JP2018-211395 | 2018-11-09 | ||
| JP2018211395A JP7113724B2 (en) | 2017-12-26 | 2018-11-09 | Method for manufacturing photomask blank and photomask, and method for manufacturing display device |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109960105A true CN109960105A (en) | 2019-07-02 |
Family
ID=67023293
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811515759.8A Pending CN109960105A (en) | 2017-12-26 | 2018-12-12 | The manufacturing method of photomask blank and photomask, the manufacturing method of display device |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP7335400B2 (en) |
| KR (1) | KR20190078506A (en) |
| CN (1) | CN109960105A (en) |
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| CN112578629A (en) * | 2019-09-30 | 2021-03-30 | 爱发科成膜株式会社 | Mask blank and photomask |
| US20210405520A1 (en) * | 2020-06-30 | 2021-12-30 | Shin-Etsu Chemical Co., Ltd. | Photomask blank, and manufacturing method thereof |
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Also Published As
| Publication number | Publication date |
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| JP7335400B2 (en) | 2023-08-29 |
| JP2022136193A (en) | 2022-09-15 |
| KR20190078506A (en) | 2019-07-04 |
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