CN109782525A - Mask substrate and its manufacturing method, phase shifting mask and its manufacturing method - Google Patents
Mask substrate and its manufacturing method, phase shifting mask and its manufacturing method Download PDFInfo
- Publication number
- CN109782525A CN109782525A CN201811051930.4A CN201811051930A CN109782525A CN 109782525 A CN109782525 A CN 109782525A CN 201811051930 A CN201811051930 A CN 201811051930A CN 109782525 A CN109782525 A CN 109782525A
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- Prior art keywords
- layer
- chemicals
- mask
- film
- mask substrate
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- Granted
Links
- 239000000758 substrate Substances 0.000 title claims abstract description 154
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 65
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 158
- 238000002310 reflectometry Methods 0.000 claims abstract description 125
- 239000000126 substance Substances 0.000 claims abstract description 124
- 230000010363 phase shift Effects 0.000 claims abstract description 91
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 79
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 64
- 239000001301 oxygen Substances 0.000 claims description 64
- 229910052760 oxygen Inorganic materials 0.000 claims description 64
- 239000007789 gas Substances 0.000 claims description 61
- 230000036961 partial effect Effects 0.000 claims description 28
- 230000003595 spectral effect Effects 0.000 claims description 14
- 229910021332 silicide Inorganic materials 0.000 claims description 6
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 claims description 6
- 239000010410 layer Substances 0.000 description 260
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 49
- 229910016006 MoSi Inorganic materials 0.000 description 39
- 229910052751 metal Inorganic materials 0.000 description 30
- 239000002184 metal Substances 0.000 description 30
- 239000011521 glass Substances 0.000 description 29
- 238000000034 method Methods 0.000 description 26
- 238000004544 sputter deposition Methods 0.000 description 26
- 239000000463 material Substances 0.000 description 17
- 229910052710 silicon Inorganic materials 0.000 description 17
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 15
- 229910002092 carbon dioxide Inorganic materials 0.000 description 15
- 239000010703 silicon Substances 0.000 description 15
- 229910052804 chromium Inorganic materials 0.000 description 13
- 239000011651 chromium Substances 0.000 description 13
- 230000008569 process Effects 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 11
- 230000008859 change Effects 0.000 description 11
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 9
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 9
- 150000002739 metals Chemical class 0.000 description 9
- 229910052750 molybdenum Inorganic materials 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 7
- 229910045601 alloy Inorganic materials 0.000 description 7
- 239000000956 alloy Substances 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 6
- 238000005530 etching Methods 0.000 description 6
- 238000011068 loading method Methods 0.000 description 6
- 230000008033 biological extinction Effects 0.000 description 5
- 238000011835 investigation Methods 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000002356 single layer Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- 229910052721 tungsten Inorganic materials 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 150000004767 nitrides Chemical class 0.000 description 4
- 239000001272 nitrous oxide Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229920002120 photoresistant polymer Polymers 0.000 description 4
- 239000012495 reaction gas Substances 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- MEYZYGMYMLNUHJ-UHFFFAOYSA-N tunicamycin Natural products CC(C)CCCCCCCCCC=CC(=O)NC1C(O)C(O)C(CC(O)C2OC(C(O)C2O)N3C=CC(=O)NC3=O)OC1OC4OC(CO)C(O)C(O)C4NC(=O)C MEYZYGMYMLNUHJ-UHFFFAOYSA-N 0.000 description 4
- 229910052726 zirconium Inorganic materials 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000000149 penetrating effect Effects 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 229910052715 tantalum Inorganic materials 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000001449 potential sputter etching Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 230000032258 transport Effects 0.000 description 2
- 238000001039 wet etching Methods 0.000 description 2
- PLXMOAALOJOTIY-FPTXNFDTSA-N Aesculin Natural products OC[C@@H]1[C@@H](O)[C@H](O)[C@@H](O)[C@H](O)[C@H]1Oc2cc3C=CC(=O)Oc3cc2O PLXMOAALOJOTIY-FPTXNFDTSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910020968 MoSi2 Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical group [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- -1 ammonium acid fluoride Fluorine compounds Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003667 anti-reflective effect Effects 0.000 description 1
- CXOWYMLTGOFURZ-UHFFFAOYSA-N azanylidynechromium Chemical compound [Cr]#N CXOWYMLTGOFURZ-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
- G03F1/26—Phase shift masks [PSM]; PSM blanks; Preparation thereof
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
- G03F1/52—Reflectors
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/70—Microphotolithographic exposure; Apparatus therefor
- G03F7/70691—Handling of masks or workpieces
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/70—Microphotolithographic exposure; Apparatus therefor
- G03F7/708—Construction of apparatus, e.g. environment aspects, hygiene aspects or materials
- G03F7/7095—Materials, e.g. materials for housing, stage or other support having particular properties, e.g. weight, strength, conductivity, thermal expansion coefficient
- G03F7/70958—Optical materials or coatings, e.g. with particular transmittance, reflectance or anti-reflection properties
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Epidemiology (AREA)
- Public Health (AREA)
- Preparing Plates And Mask In Photomechanical Process (AREA)
- Physical Vapour Deposition (AREA)
Abstract
The present invention provides a kind of mask substrate and its manufacturing method, phase shifting mask and its manufacturing method.Mask substrate of the invention is the mask substrate with the layer for becoming phase shifting mask, and the mask substrate includes the phase shift layer and antiradar reflectivity layer of stacking on the transparent substrate；With chemicals-resistant layer, it is arranged in than the phase shift layer and the antiradar reflectivity layer further from the position of the transparent substrate and chemical-resistant is improved, the Nitrogen content in the chemicals-resistant layer is set to higher than the Nitrogen content of the antiradar reflectivity layer.
Description
Technical field
It is suitble to the present invention relates to a kind of in mask substrate, phase shifting mask, the manufacturing method of mask substrate and phase shifting mask
Technology used in manufacturing method.
Background technique
As the height of flat-panel monitor (flat panel display, FPD) is detailed-oriented, the demand of fine pattern is being formed just
It is improving.Therefore, the mask of the photomask used all the time is not used only, and uses the phase shifting mask of edge enhancement type
(PSM mask) (referring to patent document 1).
This phase shifting mask requires to reduce reflectivity.
Patent document 1: public table WO2004/070472 bulletin again
This phase shifting mask preferably reduces reflectivity in exposure, it is therefore desirable to which the low film of refractive index is formed in surface.
In order to obtain the low film of refractive index in phase shifting mask, it is preferred to use the oxidation film being made of the metal through peroxidating.
On the other hand, it for the polluter of the removal influence optical characteristics from mask, needs using acid or alkalinity
Chemical liquid cleans mask.The known metal film in the cleaning process through aoxidizing is poor to the patience of aqueous slkali.
However, for the metal film used in phase shifting mask, it is known that promote film oxidation with to the resistance to of aqueous slkali
Property (chemically-resistant is fluid) between have shifting relationship.
In phase shifting mask, it is desirable that while realizing that reflectivity is smaller and the fluid stronger phase shift film of chemically-resistant.
Summary of the invention
The present invention is to propose in view of the foregoing, the purpose is to realize it is a kind of and meanwhile have lesser reflectivity and compared with
The fluid phase shift film of strong chemically-resistant.
Mask substrate involved in the 1st aspect of the present invention solves the above subject by the following technical programs.A kind of mask
Substrate, has the layer as phase shifting mask, and the mask substrate includes the phase shift layer and antiradar reflectivity of stacking on the transparent substrate
Layer；With chemicals-resistant layer, it is arranged in than the phase shift layer and the antiradar reflectivity layer further from the position of the transparent substrate
And chemical-resistant is improved, the Nitrogen content in the chemicals-resistant layer is set to the Nitrogen content than the antiradar reflectivity layer
It is high.
In the mask substrate involved in the 1st aspect of the present invention, the rate of oxygen of the preferably described antiradar reflectivity layer is set
It is high for the rate of oxygen than the chemicals-resistant layer.
For the mask substrate involved in the 1st aspect of the present invention, in the chemicals-resistant layer and the antiradar reflectivity
In layer, spectral reflectance can have downwardly projecting profile near wavelength 400nm.
In addition, the antiradar reflectivity layer is at wavelength 405nm in the mask substrate involved in the 1st aspect of the present invention
Refractive index can be set to 2.2 or less.
In addition, the chemicals-resistant layer is at wavelength 405nm in the mask substrate involved in the 1st aspect of the present invention
Refractive index can be set to 2.4 or more.
In addition, in the mask substrate involved in the 1st aspect of the present invention, the chemicals-resistant layer and the low reflection
Rate layer can be made of silicide.
In addition, in the mask substrate involved in the 1st aspect of the present invention, the Nitrogen content of the chemicals-resistant layer can be with
It is 36atm% or more.
In addition, in the mask substrate involved in the 1st aspect of the present invention, the Nitrogen content of the antiradar reflectivity layer can be with
It is 35atm% or less and rate of oxygen is 30atm% or more.
In addition, the film thickness of the chemicals-resistant layer can be in the mask substrate involved in the 1st aspect of the present invention
15nm or less.
In addition, in the mask substrate involved in the 1st aspect of the present invention, folding of the phase shift layer at wavelength 405nm
The rate of penetrating can be set to 2.4 or more.
In addition, the Nitrogen content of the phase shift layer can be in the mask substrate involved in the 1st aspect of the present invention
36atm% or more.
In addition, phase shifting mask involved in the 2nd aspect of the present invention uses mask substrate involved in above-mentioned first method
To manufacture.
In addition, the manufacturing method of mask substrate involved in the 3rd aspect of the present invention is involved in above-mentioned first method
The manufacturing method of mask substrate does not make nitrogen partial pressure in the film forming of the chemicals-resistant layer and the antiradar reflectivity layer each other not
Together.
In addition, in the manufacturing method of the mask substrate involved in the 3rd aspect of the present invention, in the chemicals-resistant layer
The partial pressure of oxygen-containing gas can be made different from each other when with the film forming of the antiradar reflectivity layer.
In addition, the manufacturing method of phase shifting mask involved in the 4th aspect of the present invention is involved in above-mentioned second method
The manufacturing method of phase shifting mask can make nitrogen partial pressure each other in the film forming of the chemicals-resistant layer and the antiradar reflectivity layer
It is different.
In the manufacturing method of the phase shifting mask involved in the 4th aspect of the present invention, in the chemicals-resistant layer and described
The partial pressure of oxygen-containing gas can be made different from each other when the film forming of antiradar reflectivity layer.
Mask substrate involved in the 1st aspect of the present invention is the mask substrate with the layer for becoming phase shifting mask, described
Mask substrate includes the phase shift layer and antiradar reflectivity layer of stacking on the transparent substrate；With chemicals-resistant layer, it is arranged than the phase
Layer and the antiradar reflectivity layer are moved further from the position of the transparent substrate and improving chemical-resistant, the chemicals-resistant
Nitrogen content in layer is set to higher than the Nitrogen content of the antiradar reflectivity layer.Thereby, it is possible to provide a kind of mask substrate, this is covered
Mould substrate can become the phase shifting mask with following mask layer: the mask layer has the reflectivity for being reduced to prescribed limit, and
And there is the patience to chemicals used in the processes such as cleaning and desired phase shift effect.
Here, alkaline chemical or acidic chemical can be applied as chemicals.As an example, can enumerate developer solution,
Stripper and cleaning solution etc., such as sodium hydroxide (NaOH), potassium hydroxide (KOH), tetramethylammonium hydroxide can be enumerated
(TMAH), sulfuric acid (H2SO4), sulfuric acid and hydrogen peroxide (H2O2) mixed liquor etc., but can especially enumerate sodium hydroxide solution.
In addition, as mask substrate involved in the 1st aspect of the present invention, it can be envisaged that when manufacturing FPD, polychrome wave exposes
Large size mask used in light.
In the mask substrate involved in the 1st aspect of the present invention, the rate of oxygen of the antiradar reflectivity layer is set to compare
The rate of oxygen of the chemicals-resistant layer and the phase shift layer is high, thus, it is possible to reduce the reflectivity in reflectivity, and logical
In the state of crossing chemicals-resistant layer and being reduced come film thickness caused by preventing because of chemicals, as mask layer, such as at g line (436nm)
There is antiradar reflectivity and phase shifting capability into the wave band of i line (365nm).
For the mask substrate involved in the 1st aspect of the present invention, in the chemicals-resistant layer and the antiradar reflectivity
In layer, spectral reflectance has profile downwardly projecting near 400nm.Thereby, it is possible to fill in exposures such as stepping light-dividing devices
It realizes in the wavelength region of exposure light used in setting as antiradar reflectivity needed for mask.
In addition, the antiradar reflectivity layer is at wavelength 405nm in the mask substrate involved in the 1st aspect of the present invention
Refractive index be set to 2.2 hereinafter, thus, it is possible to realize above-mentioned antiradar reflectivity.
In addition, the chemicals-resistant layer is at wavelength 405nm in the mask substrate involved in the 1st aspect of the present invention
Refractive index be set to 2.4 or more.As a result, as the film for being used as phase shifting mask, there can be necessary antiradar reflectivity and resistance to
Chemicals.
In addition, in the mask substrate involved in the 1st aspect of the present invention, the chemicals-resistant layer and the low reflection
Rate layer is made of silicide.Thereby, it is possible to obtain defined phase shifting capability and the fluid stronger film of chemically-resistant.
It is not limited to the MoSi based material being made of Mo and Si as the silicide film that can be suitable for phase mask as a result,
Metal can be enumerated and silicon (transition metal of MSi, M:Mo, Ni, W, Zr, Ti or Cr etc.), the metal and silicon that are aoxidized and nitrogenized
(MSiON), metal and silicon (MSiCO), the metal through oxidation, nitridation and carbonization and the silicon (MSiCON), warp for being aoxidized and being carbonized
Metal and silicon (MSiO) and the metal and silicon (MSiN) of via nitride of oxidation etc., and the gold that Ta, Ti, W, Mo or Zr can be enumerated etc.
The alloy (Cr or Ni can be enumerated as other metals) or packet of category, the mutual alloy of these metals or these metals and other metals
Material containing these metal or alloy and silicon.MoSi film can especially be enumerated.
In addition, in the mask substrate involved in the 1st aspect of the present invention, the Nitrogen content of the chemicals-resistant layer is
36atm% or more, thus, it is possible to realize desired chemical-resistant, such as can be by inhibiting the film thickness in cleaning process to become
It moves to prevent reflectivity and phase shifting capability from deviateing the range originally set.
In addition, in the mask substrate involved in the 1st aspect of the present invention, the Nitrogen content of the antiradar reflectivity layer is
35atm% or less and rate of oxygen are 30atm% or more, and thus, it is possible to set lower reflectivity within the limits prescribed.
In addition, the film thickness of the chemicals-resistant layer is 15nm in the mask substrate involved in the 1st aspect of the present invention
Hereinafter, preventing the reflectivity deviation set by the antiradar reflectivity layer while thus, it is possible to realize desired chemical-resistant
The range originally set.
In addition, in the mask substrate involved in the 1st aspect of the present invention, folding of the phase shift layer at wavelength 405nm
The rate of penetrating is set to 2.4 or more, and thus, it is possible to desired phase shifting capability.
In addition, the Nitrogen content of the phase shift layer is 36atm% in the mask substrate involved in the 1st aspect of the present invention
More than, thus, it is possible to desired phase shifting capability.
In addition, the phase shifting mask as involved in the 2nd aspect of the present invention uses mask involved in above-mentioned first method
Substrate manufactures, therefore can have chemical resistance and antiradar reflectivity and have desired phase shifting capability.
In addition, the manufacturing method of mask substrate involved in the 3rd aspect of the present invention is involved in above-mentioned first method
The manufacturing method of mask substrate does not make nitrogen partial pressure in the film forming of the chemicals-resistant layer and the antiradar reflectivity layer each other not
Together.As a result, by forming chemicals-resistant layer and antiradar reflectivity layer with defined Nitrogen content, can manufacture special with defined film
The mask substrate of property.
In addition, in the manufacturing method of the mask substrate involved in the 3rd aspect of the present invention, in the chemicals-resistant layer
Keep the partial pressure of oxygen-containing gas different from each other when with the film forming of the antiradar reflectivity layer.As a result, by with defined rate of oxygen come shape
At chemicals-resistant layer and antiradar reflectivity layer, the mask substrate with defined membrane property can be manufactured.
In addition, the manufacturing method of phase shifting mask involved in the 4th aspect of the present invention is involved by above-mentioned second embodiment
And phase shifting mask manufacturing method, make nitrogen partial pressure each other in the film forming of the chemicals-resistant layer and the antiradar reflectivity layer
It is different.The phase shifting mask that there is desired membrane property thereby, it is possible to manufacture each layer.
In the manufacturing method of the phase shifting mask involved in the 4th aspect of the present invention, in the chemicals-resistant layer and described
Make the partial pressure of oxygen-containing gas different from each other when the film forming of antiradar reflectivity layer.Thereby, it is possible to manufacture each layer with desired film
The phase shifting mask of characteristic.
Mode of the invention can bring following effect: can provide a kind of with chemical-resistant and antiradar reflectivity
And mask substrate and phase shifting mask with defined phase shift performance.
Detailed description of the invention
Fig. 1 is the sectional view of mask substrate involved in expression first embodiment of the invention.
Fig. 2 is the sectional view of phase shifting mask involved in expression first embodiment of the invention.
Fig. 3 is to indicate in the mask substrate involved in first embodiment of the invention and the manufacturing method of phase shifting mask
Film formation device schematic diagram.
Fig. 4 is to indicate in the mask substrate involved in first embodiment of the invention and the manufacturing method of phase shifting mask
Film formation device schematic diagram.
Fig. 5 is the system for indicating the mask substrate involved in first embodiment of the invention, phase shifting mask, mask substrate
The N of the NaOH for making in method and the manufacturing method of phase shifting mask treated transmissivity variation2Figure of/Ar the gas than dependence
Table.
Fig. 6 is the system for indicating the mask substrate involved in first embodiment of the invention, phase shifting mask, mask substrate
The chart of the nitrogen concentration dependence of the NaOH for making in method and the manufacturing method of phase shifting mask treated transmissivity variation.
Fig. 7 is the system for indicating the mask substrate involved in first embodiment of the invention, phase shifting mask, mask substrate
The CO of the NaOH for making in method and the manufacturing method of phase shifting mask treated transmissivity variation2The chart of concentration dependent.
Fig. 8 is the system for indicating the mask substrate involved in first embodiment of the invention, phase shifting mask, mask substrate
Make the chart of the wavelength dependency of method and the refractive index in the manufacturing method of phase shifting mask.
Fig. 9 is the system for indicating the mask substrate involved in first embodiment of the invention, phase shifting mask, mask substrate
Make the chart of the wavelength dependency of method and the extinction coefficient in the manufacturing method of phase shifting mask.
Figure 10 is to indicate the mask substrate involved in first embodiment of the invention, phase shifting mask, mask substrate
Spectral reflectance in manufacturing method and the manufacturing method of phase shifting mask and chemicals-resistant layer/antiradar reflectivity layer film thickness characteristic it
Between relationship chart.
Figure 11 is to indicate the mask substrate involved in first embodiment of the invention, phase shifting mask, mask substrate
Spectral reflectance in manufacturing method and the manufacturing method of phase shifting mask and chemicals-resistant layer/antiradar reflectivity layer film thickness characteristic it
Between relationship chart.
Specific embodiment
In the following, based on attached drawing to mask substrate involved in first embodiment of the invention, phase shifting mask, mask substrate
Manufacturing method and the manufacturing method of phase shifting mask be illustrated.
Fig. 1 is the sectional view for indicating the mask substrate in present embodiment, and Fig. 2 is to indicate that the phase shift in present embodiment is covered
The sectional view of mould, appended drawing reference 10B is mask substrate in figure.
It is that 365nm~436nm is left that mask substrate 10B involved in present embodiment, which is provided to the wavelength in exposure light,
The phase shifting mask used in right range.As shown in Figure 1, mask substrate 10B by glass substrate 11 (transparent substrate), be formed in this
It phase shift layer 12 on glass substrate 11, the antiradar reflectivity layer 13 being formed on phase shift layer 12 and is formed on antiradar reflectivity layer 13
Chemicals-resistant layer 14 constructs.These phase shift layers 12, antiradar reflectivity layer 13 and chemicals-resistant layer 14 are constituted as the low anti-of mask layer
Penetrate phase shift film.
In addition, mask substrate 10B involved in present embodiment is also possible to except phase shift layer 12, antiradar reflectivity layer 13 and resistance to
Other than chemical layer 14, the structure of matcoveredn, light shield layer and resist layer etc. is also laminated.
Transparent and excellent optical isotropy material can be used in transparent substrate 11, such as quartz glass substrate can be used
Plate.The size of transparent substrate 11 is not particularly limited, can be according to the substrate (such as LCD (liquid crystal display for using the mask exposure
Device), the FPD substrate of plasma scope or organic EL (electroluminescent) display etc. etc.) appropriate selection.
As phase shift layer 12 and chemicals-resistant layer 14, nitrogenous silicide film can be enumerated, for example, containing Ta, Ti, W, Mo or
The film of the metal of Zr etc. or alloy and silicon containing these metals, especially MoSiX (X >=2) film is (for example, MoSi2Film,
MOSi3Film or MoSi4Film etc.).
In addition, as antiradar reflectivity layer 13, it is same as phase shift layer 12 and chemicals-resistant layer 14, nitrogenous silicide can be used
Film, it is also possible to use oxygen containing film.
The present inventor by further investigation as a result, it has been found that, about the composition of MoSi film, the Mo in the ratio of components of Mo and Si
The more high then MoSi film of ratio metalline it is higher, therefore transmissivity wavelength dependency decline.Thus recognize MoSiX film
In the value of X be preferably 3 hereinafter, the value of X is more preferably 2.5 or less.Then, the value for using X in our current research is 2.3
Target.
In the present embodiment, the Nitrogen content (nitrogen concentration) of phase shift layer 12 is preferably 36atm% or more, the nitrogen of phase shift layer 12
Concentration is more preferably 40atm% or more.
In addition, the nitrogen concentration of antiradar reflectivity layer 13 is preferably 35atm% hereinafter, the nitrogen concentration of antiradar reflectivity layer 13 is more excellent
It is selected as 30atm% or less.
In addition, the nitrogen concentration of chemicals-resistant layer 14 is preferably 36atm% or more, the nitrogen concentration of chemicals-resistant layer 14 is more excellent
It is selected as 40atm% or more, the film thickness of chemicals-resistant layer 14 is preferably 20nm hereinafter, more preferably 15nm or less.In addition, chemically-resistant
The film thickness of product layer 14 is also possible to 0nm or more, preferably 5nm or more.
Meanwhile in the present embodiment, the rate of oxygen (oxygen concentration) of antiradar reflectivity layer 13 is preferably 25atm% or more, low
The rate of oxygen of reflectivity 13 is more preferably 30atm% or more.
At this point, the oxygen concentration of phase shift layer 12 can be 7.0~10atm%, the oxygen concentration of chemicals-resistant layer 14 can be 7.0
~10atm%.
In the manufacturing method of mask substrate in present embodiment, phase shift layer is carried out on glass substrate 11 (transparent substrate)
After 12 film forming, the film forming of antiradar reflectivity layer 13 and chemicals-resistant layer 14 is carried out.
Protective layer, light shield layer, counnter attack is also being laminated other than phase shift layer 12, antiradar reflectivity layer 13 and chemicals-resistant layer 14
In the case where penetrating layer and resist layer etc., mask substrate manufacturing method can have the lamination process of these layers.
As an example, such as the light shield layer comprising chromium can be enumerated.
As shown in Fig. 2, phase shifting mask 10 in present embodiment can pass through the phase shift layer 12, low anti-in mask substrate 10B
It penetrates on rate layer 13 and chemicals-resistant layer 14 and is patterned to obtain.
In the following, being said to the manufacturing method of the manufacture phase shifting mask 10 of the mask substrate 10B as involved in present embodiment
It is bright.
Photoresist layer is formed in the outmost surface of mask substrate 10B.Photoresist layer can be eurymeric, can also be minus.Photoresist layer
Liquid resist can be used.
Next, by being exposed and developing to photoresist layer come anti-in formation more outward compared with chemicals-resistant layer 14
Lose agent pattern.Resist pattern plays function as the etching mask of phase shift layer 12, antiradar reflectivity layer 13 and chemicals-resistant layer 14
Can, shape is suitably determined according to the etched pattern of phase shift layer 12, antiradar reflectivity layer 13 and chemicals-resistant layer 14.As an example,
It is set as the shape with opening width corresponding with the opening width size of phase-shift pattern is formed by phase shift field.
Next, across the resist pattern, come wet etching phase shift layer 12, antiradar reflectivity layer 13 and resistance to using etching solution
Chemical layer 14, to form phase-shift pattern 12P, 13P, 14P.It is in phase shift layer 12, antiradar reflectivity layer 13 and chemicals-resistant layer 14
In the case where MoSi, as etching solution, it is preferable to use comprising selected from least one of hydrofluoric acid, fluosilicic hydracid and ammonium acid fluoride
Fluorine compounds and etching solution selected from least one of hydrogen peroxide, nitric acid and sulfuric acid oxidant.
Further, in the case where mask substrate 10B is by forming other films such as light shield layer to constitute, by using right
The wet etching etc. for the etching solution answered forms the pattern of regulation shape corresponding with phase-shift pattern 12P, 13P, 14P to the film.It hides
The patterning of other films such as photosphere can by with its lamination order accordingly, as phase shift layer 12, antiradar reflectivity layer 13 and resistance toization
Process as defined in the patterned front and back of product layer 14 carries out.
The phase shifting mask 10 with phase-shift pattern 12P, 13P, 14P as shown in Figure 2 is obtained by above step.
In the following, the manufacturing method based on the mask substrate in Detailed description of the invention present embodiment.
Fig. 3 is the schematic diagram for indicating the manufacturing device of the mask substrate in present embodiment, and Fig. 4 is to indicate present embodiment
In mask substrate manufacturing device schematic diagram.
Mask substrate 10B in present embodiment is manufactured by Fig. 3 or manufacturing device shown in Fig. 4.
Manufacturing device S10 shown in Fig. 3 is reciprocating sputtering equipment, has loading and relief chamber S11 and passes through sealing
The film forming room S12 (vacuum processing chamber) that S13 is connect with loading and relief chamber S11.
Be provided in loading and relief chamber S11 will be transported from the glass substrate 11 that is transported into of outside to film forming room S12 or
The rotation of the external conveyer S11a transported to film forming room S12 and the inside pumping black vacuum to the loading and relief chamber S11
The exhaust apparatus S11b of pump etc..
It is provided with base plate keeping device S12a in film forming room S12, is sent out with the supply unit as supply filmogen
Wave the target S12b of function cathode electrode S12c (backboard), to backboard S12c apply negative potential sputtering voltage power supply S12d, to
The gas leading-in device S12e of gas and the turbine point of the inside pumping high vacuum to film forming room S12 are imported in film forming room S12
The high vacuum exhausting apparatus S12f of son pump etc..
The glass substrate 11 shipped by conveyer S11a can be remained the glass base by base plate keeping device S12a
Plate 11 is opposite with target S12b in film forming, and can by glass substrate 11 from load and relief chamber S11 be transported into and to load and
Relief chamber S11 is transported.
Target S12b is constituted the required material formed that form a film of glass substrate 11 by having.
In manufacturing device S10 shown in Fig. 3, glass substrate 11 is transported into manufacturing device S10 by loading and relief chamber S11
Inside.Later, it is formed a film by sputtering to glass substrate 11 in film forming room S12 (vacuum processing chamber).Later, from loading
And relief chamber S11 transports the glass substrate S11 for terminating film forming to the outside of manufacturing device S10.
In film formation process, sputter gas and reaction gas are supplied from gas leading-in device S12e to film forming room S12, by outer
Portion's power supply applies sputtering voltage to backboard S12c (cathode electrode).Furthermore, it is also possible to by magnetron magnetic circuit come on target S12b
Magnetic field as defined in being formed.In film forming room S12, pass through the ion of the sputter gas of plasma excitation and cathode electrode S12c
Target S12b is collided, so that the particle of filmogen be made to fly out.Also, the particle to fly out is attached to glass later in conjunction with reaction gas
On glass substrate 11, thus film as defined in being formed on the surface of glass substrate 11.
At this point, importing and filling from gas in the film formation process of phase shift layer 12 and chemicals-resistant layer 14 and antiradar reflectivity layer 13
It sets S12e and supplies different amounts of nitrogen and oxygen-containing gas, and in order to control the partial pressure of the gas, gas flow is changed, thus by phase
The composition for moving layer 12, chemicals-resistant layer 14 and antiradar reflectivity layer 13 is set within the set range.
Here, CO can be enumerated as oxygen-containing gas2(carbon dioxide), O2(oxygen), N2O (nitrous oxide) and a NO (oxygen
Change nitrogen) etc..
In addition, in the film formation process of phase shift layer 12, chemicals-resistant layer 14 and antiradar reflectivity layer 13, if necessary to can also be with
Replace target S12b.
It further, can be with shape on the film-forming base of these phase shift layers 12, antiradar reflectivity layer 13 and chemicals-resistant layer 14
At the stacked film being layered on these layers.In this case, it is possible to adjust the target used in the film forming of stacked film and gas etc.
Sputtering condition, and form stacked film by sputtering, other film build methods also can be used.By being thusly-formed stacked film
To obtain mask substrate 10B involved in present embodiment.
Moreover, manufacturing device S20 shown in Fig. 4 is in-line arrangement sputtering equipment.The sputtering equipment has load chamber S21, leads to
Cross the film forming room S22 (vacuum processing chamber) and connect by sealing S24 and film forming room S22 that sealing S23 is connect with load chamber S21
The relief chamber S25 connect.
The conveyer for transporting the glass substrate 11 being transported into from outside to film forming room S22 is provided in load chamber S21
The S21a and exhaust apparatus S21b that rotary pump of black vacuum etc. is taken out to the inside of load chamber S21.
It is provided with base plate keeping device S22a in film forming room S22, is sent out with the supply unit as supply filmogen
Wave the target S22b of function cathode electrode S22c (backboard), to backboard S22c apply negative potential sputtering voltage power supply S22d, to
The gas leading-in device S22e of gas and the turbine point of the inside pumping high vacuum to film forming room S22 are imported in film forming room S22
The high vacuum exhausting apparatus S22f of son pump etc..
The glass substrate 11 shipped by conveyer S21a is remained the glass substrate 11 by base plate keeping device S22a
It is opposite with target S22b in film forming.Further, base plate keeping device S22a can by glass substrate 11 from load chamber S21 be transported into
And it is transported to relief chamber S25.
Target S22b is constituted the required material formed that form a film of glass substrate 11 by having.
The conveyer that the glass substrate 11 that will be transported into from film forming room S22 is transported to outside is provided in relief chamber S25
The S25a and exhaust apparatus S25b that rotary pump of black vacuum etc. is taken out to the inside of relief chamber S25.
In manufacturing device S20 shown in Fig. 4, glass substrate 11 is transported into the interior of manufacturing device S20 by load chamber S21
Portion.Later, it is formed a film by sputtering to glass substrate 11 in film forming room S22 (vacuum processing chamber).Later, from relief chamber
S25 transports the glass substrate 11 for terminating film forming to the outside of manufacturing device S20.
In film formation process, sputter gas and reaction gas are supplied from gas leading-in device S22e to film forming room S22, and
Sputtering voltage is applied to backboard S22c (cathode electrode) by external power supply.Alternatively, it is also possible to pass through magnetron magnetic circuit in target S22b
Magnetic field as defined in upper formation.In film forming room S22, pass through the ion and cathode electrode S22c of the sputter gas of plasma excitation
Target S22b collide, so that the particle of filmogen be made to fly out.Also, the particle to fly out is attached to later in conjunction with reaction gas
On glass substrate 11, thus film as defined in being formed on the surface of glass substrate 11.
At this point, importing and filling from gas in the film formation process of phase shift layer 12 and chemicals-resistant layer 14 and antiradar reflectivity layer 13
It sets S22e and supplies different amounts of nitrogen and oxygen-containing gas, and in order to control the partial pressure of the gas, gas flow is changed, thus by phase
The composition for moving layer 12, chemicals-resistant layer 14 and antiradar reflectivity layer 13 is set within the set range.
Here, CO can be enumerated as oxygen-containing gas2(carbon dioxide), O2(oxygen), N2O (nitrous oxide) or NO (one
Nitrogen oxide) etc..
In addition, in the film formation process of phase shift layer 12, chemicals-resistant layer 14 and antiradar reflectivity layer 13, if necessary to can also be with
Replace target S22b.
It further, can also be with shape on the film-forming base of these phase shift layers 12, chemicals-resistant layer 14 and antiradar reflectivity layer 13
At the stacked film being layered on these layers.In this case, it is possible to adjust target and gas used in the film forming of stacked film etc.
Sputtering condition, and stacked film is formed by sputtering, other film build methods also can be used.By be thusly-formed stacked film come
Obtain mask substrate 10B involved in present embodiment.
In the following, the membrane property progress to phase shift layer 12, antiradar reflectivity layer 13 and chemicals-resistant layer 14 in present embodiment
Explanation.
Here, in order to illustrate phase shift layer 12, antiradar reflectivity layer 13 and chemicals-resistant layer 14 are set as being made of MoSi
Film, but not limited to this.
As the phase shift layer 12 of low reflection phase shift film, antiradar reflectivity layer 13 and chemicals-resistant involved in present embodiment
In layer 14, the nitrogen concentration in antiradar reflectivity layer 13 is set below the nitrogen concentration of phase shift layer 12 and chemicals-resistant layer 14.
Specifically, by changing the N when film forming based on sputtering2Partial pressure, such as antiradar reflectivity layer 13 is formed a film as nitrogen
The MoSi film below of concentration 30%.
By changing the N when film forming based on sputtering2Partial pressure, for example, by chemicals-resistant layer 14 form a film for nitrogen concentration 40% with
On MoSi film.
By changing the N when film forming based on sputtering2Partial pressure, such as phase shift layer 12 is formed a film as 40% or more nitrogen concentration
MoSi film.In addition, in order to function phase shift layer 12 as necessary phase-shifter, phase shift layer 12 can be set as and chemically-resistant
The different nitrogen partial pressure of product layer 14.
In addition, as the phase shift layer 12 of low reflection phase shift film, antiradar reflectivity layer 13 involved in present embodiment and resistance to
In chemical layer 14, the oxygen concentration in antiradar reflectivity layer 13 is set to be higher than phase shift layer 12 and the oxygen of chemicals-resistant layer 14 is dense
Degree.
The CO of oxygen-containing gas when specifically, by changing as film forming based on sputtering2Partial pressure, such as by low reflection
The film forming of rate layer 13 is the MoSi film of 30% or more oxygen concentration.
The CO of oxygen-containing gas when by changing as film forming based on sputtering2Partial pressure, for example, by chemicals-resistant layer 14 at
Film is the MoSi film below of oxygen concentration 30%.
The CO of oxygen-containing gas when by changing as film forming based on sputtering2Partial pressure, such as be by the film forming of phase shift layer 12
The MoSi film below of oxygen concentration 30%.In addition, in order to make phase shift layer 12 that necessary phase-shifter is used as to function, it can be by phase shift
Layer 12 is set as the oxygen-containing gas partial pressure different from chemicals-resistant layer 14.
Here, the membrane property variation that verifying is generated by the changes of contents of nitrogen and oxygen.
Firstly, the transmissivity variation that verifying is generated by nitrogen content variation.As an example, it is shown in table 1 and is based in change
The N when film forming of sputtering2The ratio of components of MoSi film single layer in the case where partial pressure changes.
[table 1]
As shown in table 1, it is thus understood that when the ratio of components of nitrogen generates variation, generate the variation of transmissivity therewith.As this
In the phase shift layer 12 of low reflection phase shift film, antiradar reflectivity layer 13 and chemicals-resistant layer 14 involved in embodiment, this can be utilized
One situation has defined transmissivity to set phase shift film.
Next, the chemical-resistant that verifying is generated by nitrogen content variation.
Fig. 5 is that treated that transmissivity changes by the NaOh that indicates in low reflection phase shift film involved in present embodiment
N2/ Ar gas than dependence chart, Fig. 6 be indicate in low reflection phase shift film involved in present embodiment NaOH processing after
Transmissivity variation nitrogen concentration dependence chart, Fig. 7 indicates in low reflection phase shift film involved in present embodiment
The CO of NaOH treated transmissivity variation2The chart of concentration dependent.
As an example, based on sputtering and by changing N2Partial pressure and in the above-mentioned MoSi film single layer that forms a film, investigation
Carry out the transmissivity variation under the 405nm before and after base extraction.
Here, treatment conditions are as follows: NaOH concentration 5%, temperature are 40 DEG C, and dip time changes in 15~60 minutes
Become.In addition, gas condition when as film forming, the N with table 12Partial pressure is accordingly shown N2: Ar flow-rate ratio.
Recognize from its result with following nitrogen partial pressure dependence: as shown in Figures 5 and 6, changing from nitrogen partial pressure 100%
Transmission in the case where becoming nitrogen partial pressure 0%, according to NaOH treated Thickness Variation, as nitrogen partial pressure becomes smaller, at 405nm
Rate changes greatly.
It is thus understood that with following Thickness Variation and nitrogen concentration dependence: in the feelings that nitrogen concentration is 40atm% or more
Under condition, the transmissivity variation at 405nm can almost be ignored.
Next, verifying is because of CO2The chemical-resistant that partial pressure variation generates.
As an example, CO when changing the film forming based on sputtering is shown in table 22MoSi film single layer in the case where partial pressure
Ratio of components variation.Here, N2Partial pressure and Ar partial pressure are 10:0, only by CO2Partial pressure changes in 1~10sccm of flow.
[table 2]
Next, based on sputtering and by changing CO2Partial pressure and in the above-mentioned MoSi film single layer that forms a film, investigation
Transmissivity variation under 405nm before and after progress base extraction.
Here, treatment conditions are as follows: NaOH concentration 5%, temperature are 40 DEG C, and dip time changes in 15~60 minutes
Become.
Recognize from the result with following oxygen dependence: as shown in fig. 7, only by CO2Partial pressure flow 1~
In the case where changing in 10sccm, according to NaOH treated Thickness Variation, with CO2Gas flow becomes larger, at 405nm
Transmissivity becomes larger.
It is thus understood that having following Thickness Variation and oxygen concentration dependence: the oxygen concentration in chemicals-resistant layer 14
In the case where less, the transmissivity variation at 405nm can almost be ignored.
Next, verifying wavelength dependency.
Fig. 8 is the chart for indicating the wavelength dependency of the refractive index in phase shift film involved in present embodiment, and Fig. 9 is table
Show the chart of the wavelength dependency of the extinction coefficient in phase shift film involved in present embodiment.
As an example, based on sputtering and by changing CO2Partial pressure and in the above-mentioned MoSi film single layer that forms a film, investigation
The wavelength dependency of refractive index and extinction coefficient.
Recognize from the result with following CO2Gas flow dependence: as shown in figure 8, in CO2Gas flow from
In the case that 1sccm changes into 10sccm, with CO2Gas flow becomes larger, and the variations in refractive index under each wavelength becomes smaller, and such as
Shown in Fig. 9, extinction coefficient becomes smaller.
Next, verifying spectral reflectance variation.
Figure 10 is the spectral reflectance and chemicals-resistant layer/antiradar reflectivity indicated in phase shift film involved in present embodiment
The chart of relationship between the film thickness characteristic of layer, Figure 11 are the spectral reflectance indicated in phase shift film involved in present embodiment
The chart of relationship between chemicals-resistant layer/antiradar reflectivity layer film thickness characteristic.
As an example, it in the antiradar reflectivity layer 13 and chemicals-resistant layer 14 being made of MoSi, has investigated by chemically-resistant
The film thickness of product layer 14 changes into 0nm~20nm, under the 405nm when film thickness of antiradar reflectivity layer 13 to be changed into 0nm or 40nm
The film thickness dependence of spectral reflectance.
Its result is shown in FIG. 10.
It is shown in figure A；Chemicals-resistant tunic thickness/B；Antiradar reflectivity tunic is thick.
In addition, the nitrogen concentration in antiradar reflectivity layer 13 at this time is 29.5atm% (N when film forming2Partial pressure is
30%), the oxygen concentration in antiradar reflectivity layer 13 is 23.0atm% (CO when film forming2Gas flow is 5sccm), chemicals-resistant
Nitrogen concentration in layer 14 is 49.9atm% (N when film forming2Partial pressure is 100%), the oxygen concentration in chemicals-resistant layer 14 is
9.9atm% (CO when film forming2Gas flow is 0sccm).
In the stacking of these MoSi films, continuous supply gas while nitrogen concentration can be only changed, or can be used as not
Same sputtering process changes the nitrogen partial pressure and CO of supply gas at the time of being laminated to defined film thickness2Gas flow.
Recognize in chemicals-resistant layer 14 and antiradar reflectivity layer 13 from the result, spectral reflectance has under various film thickness
There is downwardly projecting profile near 400nm.
Here, can by change chemicals-resistant layer 14 and antiradar reflectivity layer 13 film thickness, by reflectivity profile be in
The wavelength of lower protrusion is located near 400nm to the range near 500nm.
Equally, it in the antiradar reflectivity layer 13 and chemicals-resistant layer 14 being made of MoSi, has investigated by chemicals-resistant layer
14 film thickness changes into 0nm~20nm, the light splitting under the 405nm when film thickness of antiradar reflectivity layer 13 to be changed into 0nm~55nm
The film thickness dependence of reflectivity.
Its result is shown in FIG. 11.
It is shown in figure A；Chemicals-resistant tunic thickness/B；Antiradar reflectivity tunic is thick.
In addition, the nitrogen concentration in antiradar reflectivity layer 13 at this time is 29.5atm% (N when film forming2Partial pressure is
30%), the oxygen concentration in antiradar reflectivity layer 13 is 23.0atm% (CO when film forming2Gas flow is 5sccm), chemicals-resistant
Nitrogen concentration in layer 14 is 49.9atm% (N when film forming2Partial pressure is 100%), the oxygen concentration in chemicals-resistant layer 14 is
9.9atm% (CO when film forming2Gas flow is 0sccm).
From this as a result, in chemicals-resistant layer 14 and antiradar reflectivity layer 13, spectral reflectance has under various film thickness
Downwardly projecting profile near 400nm, and can be set by the film thickness of setting chemicals-resistant layer 14 and antiradar reflectivity layer 13
It is set to reflectivity profile to concentrate near 400nm in downwardly projecting wavelength.
So, it is thus understood that can reduce and reflect in desired wavelength region by using embodiments of the present invention
Rate.
In the present embodiment, the phase shift layer 12, antiradar reflectivity layer 13 and the chemicals-resistant layer 14 that are made of MoSi at
When film, by controlling N2Partial pressure and CO2Its film thickness is divided and controlled, it is high that and chemical-resistant low with reflectivity can be manufactured
Low reflection phase shift film mask substrate 10B and phase shifting mask 10.
Moreover, following mask substrate 10B and phase shifting mask 10 can be manufactured: in order to remove influence light in cleaning process
Learn the polluter of characteristic and using acid or alkaline chemical come when cleaning mask substrate 10B and phase shifting mask 10, the mask
The patience of substrate 10B and phase shifting mask 10 is high, and film thickness changes and the variation of reflectivity along with this and transmissivity is less.
In mask substrate 10B and phase shifting mask 10 involved in the present embodiment for manufacturing FPD device, to conduct
The phase shift layer 12 being made of MoSi, antiradar reflectivity layer 13 and the chemicals-resistant layer 14 of low reflection phase shift film, change and control at
N when film2Partial pressure and CO2Partial pressure and film thickness.Only by this control, can control to be issued at least from ultrahigh pressure mercury lamp
From i line to the wave band of g line and its near, in the phase shift layer 12, antiradar reflectivity layer 13 and the chemicals-resistant layer 14 that are made of MoSi
It is best able to reduce the peak value (the downwardly projecting profile of Figure 10 and Figure 11) of reflectivity near 405nm.Thus, it is possible to be to advise
It can reduce reflectivity and the phase-shifter with phase shifting capability in fixed wave band.
In mask substrate 10B and phase shifting mask 10 involved in the present embodiment for manufacturing FPD device, as low
The material of the phase shift layer 12 being made of MoSi of reflection phase shift film, antiradar reflectivity layer 13 and chemicals-resistant layer 14 is not limited to by Mo
The MoSi based material constituted with Si.As the material, metal and the silicon (mistake of MSi, M:Mo, Ni, W, Zr, Ti or Cr etc. can be enumerated
Cross metal), the metal that is aoxidized and nitrogenized and silicon (MSiON), the metal for being aoxidized and being carbonized and silicon (MSiCO), through oxidation, nitrogen
The metal and silicon (MSiCON), the metal through aoxidizing and silicon (MSiO) and the metal and silicon (MSiN) of via nitride etc. changed and be carbonized.
In addition, the alloy that can enumerate the metal of Ta, Ti, W, Mo and Zr etc., the alloy of these metals or these metals and other metals (is made
Cr or Ni can be enumerated for other metals), the material comprising these metal or alloy and silicon.
Mask substrate 10B and phase shifting mask 10 involved in present embodiment for manufacturing FPD device can have shading
Layer.At this point, the material of light shield layer is for example preferably the material different from the etching characteristic of low reflection phase shift film, low reflection is being constituted
In the case that the metal of phase shift film is molybdenum, the material of light shield layer is preferably the carbonization of chromium, the oxide of chromium, the nitride of chromium, chromium
Object, the fluoride of chromium or the material comprising wherein at least one.Similarly, in semi-transparency film by chromium nitride membrane system material
In the case that material is constituted, the material of light shield layer is preferably the fluorination of chromium, the oxide of chromium, the nitride of chromium, the carbide of chromium, chromium
Object or material comprising wherein at least one.
The structure of light shield layer can be used relative to glass substrate 11 in configuration light shield layer more more outward than low reflection phase shift film
It is top typed or set type at the bottom for configuring light shield layer more in the inner part than low reflection phase shift film.It further, at this time can be in light shield layer
Resist layer is set between low reflection phase shift film.
Mask substrate 10B and phase shifting mask 10 involved in present embodiment for manufacturing FPD device can only pass through
Change as the phase shift layer 12 of low reflection phase shift film, the nitrogen concentration of antiradar reflectivity layer 13 and chemicals-resistant layer 14 and oxygen concentration and makes
It makes.Thus, it is possible to only by sputtering supply preset into the atmosphere gas of normal concentration (regulation flow-rate ratio) and manufacture
Mask substrate 10B and phase shifting mask 10.Thereby, it is possible to the nitrogen concentration for being easy to make in the face of low reflection phase shift film in direction and oxygen are dense
Degree uniformly, and can inhibit the variation of reflectivity, transmissivity and phase shifting capability in face in direction.
In addition, also can be set to the nitrogen of phase shift layer 12, antiradar reflectivity layer 13 and chemicals-resistant layer 14 in the present embodiment
The structure that concentration and oxygen concentration change on film thickness direction.In the case, if in order to maintain chemical-resistant, in most appearance
High nitrogen concentration is maintained in face (outer fix), then can suitably change film thickness and nitrogen concentration and oxygen concentration, as defined in maintaining
Reflectivity, transmissivity and phase shifting capability.
[embodiment]
In the following, illustrating embodiment according to the present invention.
<embodiment 1>
Using large-scale in-line arrangement sputtering equipment large-size glass substrate (synthetic quartz (QZ): with a thickness of 10mm, having a size of
850mm × 1200mm) on carry out the film forming of low reflection phase shift mask.Specifically, the MoSiX target for the use of X value being 2.3, by Ar
Gas and N2Gas forms MoSi film as sputter gas.At this point, by changing nitrogen partial pressure like that as shown in table 1, and
Nitrogen concentration is periodically changed into 44.9atm% (experimental example 1), 40.8atm% (experimental example 2), 29.5atm% (experimental example
3) and 7.2atm% (experimental example 4), to make multiple samples.
The transmissivity variation carried out under the 405nm of NaOH liquid before and after the processing has been investigated the film of above-mentioned experimental example 1~4, and
And show the result in Fig. 5 and Fig. 6.
Here, treatment conditions are as follows: NaOH concentration 5%, temperature are 40 DEG C, and dip time changes in 15~60 minutes
Become.In addition, gas condition when as film forming, the N with table 12Partial pressure is accordingly shown N2: Ar flow-rate ratio.
<embodiment 2>
Next, it is same as above-mentioned experimental example 1~4, by Ar gas, N2Gas and CO2Gas is carried out as sputter gas
The film forming of MoSi film.At this point, by changing CO as shown in Figure 72Gas flow, and oxygen concentration is periodically changed into
9.9atm% (experimental example 5), 12.7atm% (experimental example 6), 18.0atm% (experimental example 7), 34.7atm% (experimental example 8) and
47.1atm% (experimental example 9), to make multiple samples.
The transmissivity variation carried out under the 405nm of NaOH liquid before and after the processing has been investigated the film of above-mentioned experimental example 5~9, and
And show the result in Fig. 7.
Here, same as above-mentioned experimental example 1~4, treatment conditions are as follows: NaOH concentration 5%, and temperature is 40 DEG C, dipping
Time changes in 15~60 minutes.In addition, gas condition when as film forming, the N with table 12Partial pressure is accordingly shown N2:Ar
Flow-rate ratio.
Further, to the wavelength dependency of film the investigation refractive index and extinction coefficient of above-mentioned experimental example 5~9, and will knot
Fruit is shown in Fig. 8 and Fig. 9.
Recognize that chemical-resistant and transmissivity, refractive index change according to the oxygen concentration in MoSi film from these results.
Next, in order to investigate the CO as oxygen-containing film forming gas2The influence of C (carbon) in gas, to above-mentioned experimental example 5
Ratio of components of~9 film analysis containing C.It is shown in table 3 its result.
[table 3]
Recognize that concentration of carbon will not bring greater impact chemicals-resistant characteristic from these results and data.In addition,
It is functioned even if solving and can be used as anti-reflective film containing carbon.
<embodiment 3>
Next, similarly to Example 2, along film thickness direction stacking nitrogen concentration be 49.5atm% and oxygen concentration is
MoSi film, the nitrogen concentration of 6.69atm% is 29.5atm% and oxygen concentration is 36.77atm% MoSi film, nitrogen concentration are
This three layers of the MoSi film that 49.5atm% and oxygen concentration are 6.69atm%.At this point, the nitrogen concentration of the layer in order to make glass substrate side
Higher and oxygen concentration is lower, and after MoSi film becomes defined film thickness after starting film forming, change imports the N of gas2Gas point
Pressure and CO2Partial pressure, and with the N of top layer2There is partial pressure concentration the mode of the chemical-resistant in embodiment 2 to mention
High nitrogen partial pressure simultaneously forms a film.
In addition, in the state of after the different MoSi film of stacking nitrogen concentration and oxygen concentration, by the high nitrogen concentration film of top side
Film thickness be set as A, when the film thickness of second high oxygen concentration MoSi film is set as B, by A/B change into 0nm/0nm (experimental example 10),
0nm/40nm (experimental example 11), 5nm/40nm (experimental example 12), 10nm/40nm (experimental example 13), 15nm/40nm (experimental example 14)
With 20nm/40nm (experimental example 15).
The wavelength dependency for having investigated the film of above-mentioned experimental example 10~15 spectral reflectance, shows the result in Figure 10.
Equally, after the different MoSi film of stacking nitrogen concentration and oxygen concentration in the state of, by the high nitrogen concentration film of top side
Film thickness be set as A, when the film thickness of second high oxygen concentration MoSi film is set as B, by A/B change into 0nm/0nm (experimental example 10),
0nm/40nm (experimental example 11), 5nm/35nm (experimental example 16), 10nm/30nm (experimental example 17), 15nm/15nm (experimental example 18)
With 20nm/10nm (experimental example 19).
The wavelength dependency of spectral reflectance has been investigated to the film of above-mentioned experimental example 10,11,16~19, and result has been shown
In Figure 11.
Recognize from these results by changing nitrogen concentration in MoSi film and oxygen concentration through-thickness and adjusting
Its film thickness, so that the profile of the spectral reflectance in stacked film is downwardly projecting for the film thickness of the high nitrogen concentration film of top side.
Here, the profile of reflectivity can be made by making nitrogen concentration and the variation of oxygen concentration through-thickness in MoSi film
Downwardly projecting wavelength is near the 400nm in the range near 500nm.
In addition, by changing nitrogen concentration in MoSi film and oxygen concentration through-thickness and adjusting film thickness, Neng Goushe
The downwardly projecting wavelength of profile for being set to reflectivity concentrates near 400nm.
Reflectivity can be reduced in desired wavelength region by using phase shifting mask of the invention by so recognizing.
Industrial availability
As application examples of the invention, applied in all masks that can be needed in the manufacture of LCD or organic el display
The present invention.For example, can be in the mask for manufacturing TFT or colored filter etc. using the present invention.
Description of symbols
10 ... phase shifting masks
10B ... mask substrate
11 ... glass substrates (transparent substrate)
12 ... phase shift layers
13 ... antiradar reflectivity layers
14 ... chemicals-resistant layers
12P, 13P, 14P ... phase-shift pattern
S10, S20 ... film formation device (sputtering equipment)
S11 ... is loaded and relief chamber
S21 ... load chamber
S25 ... relief chamber
S11a, S21a, S25a ... conveyer (carrier robot)
S11b, S21b, S25b ... exhaust apparatus
S12, S22 ... film forming room (chamber)
S12a, S22a ... base plate keeping device
S12b, S22b ... target
S12c, S22c ... backboard (cathode electrode)
S12d, S22d ... power supply
S12e, S22e ... gas leading-in device
S12f, S22f ... high vacuum exhausting apparatus
Claims (16)
1. a kind of mask substrate, has the layer as phase shifting mask, the mask substrate is included
The phase shift layer and antiradar reflectivity layer of stacking on the transparent substrate；With
Chemicals-resistant layer, be arranged in than the phase shift layer and the antiradar reflectivity layer further from the position of the transparent substrate and
Chemical-resistant is improved,
Nitrogen content in the chemicals-resistant layer is set to higher than the Nitrogen content of the antiradar reflectivity layer.
2. mask substrate according to claim 1,
The rate of oxygen of the antiradar reflectivity layer is set to higher than the rate of oxygen of the chemicals-resistant layer.
3. mask substrate according to claim 1 or 2,
In the chemicals-resistant layer and the antiradar reflectivity layer, spectral reflectance has downwardly projecting near wavelength 400nm
Profile.
4. mask substrate according to claim 1 or 2,
Refractive index of the antiradar reflectivity layer at wavelength 405nm is set to 2.2 or less.
5. mask substrate according to claim 1 or 2,
Refractive index of the chemicals-resistant layer at wavelength 405nm is set to 2.4 or more.
6. mask substrate according to claim 1 or 2,
The chemicals-resistant layer and the antiradar reflectivity layer are made of silicide.
7. mask substrate according to claim 1 or 2,
The Nitrogen content of the chemicals-resistant layer is 36atm% or more.
8. mask substrate according to claim 1 or 2,
The Nitrogen content of the antiradar reflectivity layer is 35atm% or less and rate of oxygen is 30atm% or more.
9. mask substrate according to claim 1 or 2,
The film thickness of the chemicals-resistant layer is 15nm or less.
10. mask substrate according to claim 1 or 2,
Refractive index of the phase shift layer at wavelength 405nm is set to 2.4 or more.
11. mask substrate according to claim 1 or 2,
The Nitrogen content of the phase shift layer is 36atm% or more.
12. a kind of phase shifting mask is manufactured using mask substrate described in any one of claim 1 to 11.
13. a kind of manufacturing method of mask substrate,
The mask substrate is mask substrate described in any one of claim 1 to 11,
Keep nitrogen partial pressure different from each other in the film forming of the chemicals-resistant layer and the antiradar reflectivity layer.
14. the manufacturing method of mask substrate according to claim 13,
Keep the partial pressure of oxygen-containing gas different from each other in the film forming of the chemicals-resistant layer and the antiradar reflectivity layer.
15. a kind of manufacturing method of phase shifting mask,
The phase shifting mask is phase shifting mask described in claim 12,
Keep nitrogen partial pressure different from each other in the film forming of the chemicals-resistant layer and the antiradar reflectivity layer.
16. the manufacturing method of phase shifting mask according to claim 15,
Keep the partial pressure of oxygen-containing gas different from each other in the film forming of the chemicals-resistant layer and the antiradar reflectivity layer.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017219236A JP6998181B2 (en) | 2017-11-14 | 2017-11-14 | Mask blank, phase shift mask and its manufacturing method |
| JP2017-219236 | 2017-11-14 |
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| JP (1) | JP6998181B2 (en) |
| KR (1) | KR20190054905A (en) |
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| JP7254599B2 (en) * | 2019-04-15 | 2023-04-10 | アルバック成膜株式会社 | Method for manufacturing mask blanks and method for manufacturing phase shift mask |
| JP7303077B2 (en) * | 2019-09-10 | 2023-07-04 | アルバック成膜株式会社 | Method for manufacturing mask blanks, method for manufacturing photomask, mask blanks and photomask |
| JP7381374B2 (en) * | 2020-03-16 | 2023-11-15 | アルバック成膜株式会社 | Mask blanks, phase shift masks, manufacturing methods |
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Also Published As
| Publication number | Publication date |
|---|---|
| JP6998181B2 (en) | 2022-02-04 |
| KR20190054905A (en) | 2019-05-22 |
| JP2019090910A (en) | 2019-06-13 |
| TW201923119A (en) | 2019-06-16 |
| TWI767053B (en) | 2022-06-11 |
| CN109782525B (en) | 2023-10-27 |
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