CN104718496B - The manufacturing method of phase-shift mask - Google Patents
The manufacturing method of phase-shift mask Download PDFInfo
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- CN104718496B CN104718496B CN201380052684.3A CN201380052684A CN104718496B CN 104718496 B CN104718496 B CN 104718496B CN 201380052684 A CN201380052684 A CN 201380052684A CN 104718496 B CN104718496 B CN 104718496B
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- 230000010363 phase shift Effects 0.000 title claims abstract description 215
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 33
- 239000000758 substrate Substances 0.000 claims description 50
- 238000005530 etching Methods 0.000 claims description 32
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 238000012216 screening Methods 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229910052758 niobium Inorganic materials 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 229910052735 hafnium Inorganic materials 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 239000010410 layer Substances 0.000 description 173
- 239000011651 chromium Substances 0.000 description 33
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 14
- 150000004767 nitrides Chemical class 0.000 description 13
- 239000011521 glass Substances 0.000 description 10
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 9
- 229910052804 chromium Inorganic materials 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 238000003763 carbonization Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 238000001039 wet etching Methods 0.000 description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 7
- 230000003628 erosive effect Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 229920002120 photoresistant polymer Polymers 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 5
- 229910002651 NO3 Inorganic materials 0.000 description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 238000000059 patterning Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
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- 238000003475 lamination Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 241000208340 Araliaceae Species 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 2
- 235000003140 Panax quinquefolius Nutrition 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- -1 carbide Substances 0.000 description 2
- 239000006059 cover glass Substances 0.000 description 2
- 235000008434 ginseng Nutrition 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
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- 230000003287 optical effect Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000018199 S phase Effects 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000000231 atomic layer deposition Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- UOUJSJZBMCDAEU-UHFFFAOYSA-N chromium(3+);oxygen(2-) Chemical group [O-2].[O-2].[O-2].[Cr+3].[Cr+3] UOUJSJZBMCDAEU-UHFFFAOYSA-N 0.000 description 1
- 230000010485 coping Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
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- 238000001704 evaporation Methods 0.000 description 1
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- 238000002474 experimental method Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
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- 238000000608 laser ablation 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
- G03F1/29—Rim PSM or outrigger PSM; Preparation thereof
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Preparing Plates And Mask In Photomechanical Process (AREA)
- Engineering & Computer Science (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
Abstract
The manufacturing method of phase-shift mask is with following process: forming second exposure mask (RP2) with defined patterns of openings, so that surface and be exposed to pattern openings light shield layer (13) it is capped, and be uncovered the etch stop layer (12) for being exposed to pattern openings and phase shift layer (11) in lightproof area and capped in phase shifting region.
Description
Technical field
The present invention relates to the phase-shift masks and its manufacturing method that are capable of forming fine and high-precision exposing patterns, especially relate to
And it is suitble to the technology used in the manufacture of flat-panel monitor.
The application based on December 27th, 2012 in the Japanese Patent Application 2012-285846 CLAIM OF PRIORITY of Japanese publication,
It is hereby incorporated its content.
Background technique
In the manufacturing process of semiconductor equipment and FPD, in order to be formed in the anti-of the substrate being made of silicon or glass etc.
Fine pattern is exposed on erosion agent film, transfers and uses phase-shift mask.Since the glass substrate of FPD is than semiconductor
Silicon substrate area is big, therefore uses g line, h line and i line to be exposed with substrate of the sufficient exposure light amount to FPD
Composite wavelength exposure light.When using this exposure light, in the past always using edge enhancement type phase-shift mask (for example, ginseng
Examine patent document 1).
On the other hand, as used for realizing the method further miniaturizeing half-tone type phase shift mask (for example, ginseng
Examine patent document 2).According to this method, due to being 180 ° in 193nm phase, it is thus possible to set position of the luminous intensity as zero with
Improve patterning precision.Moreover, because there are the positions that luminous intensity is zero, it is thus possible to which the depth of focus is set to larger, reality
Existing conditions of exposure relax or patterned yield rate improves.
However, being carried out in above-mentioned conventional example by forming a film on the transparent substrate to light shield layer, and to the light shield layer
It etches and patterns, and form a film phase shift layer to cover and pass through patterned light shield layer, and the phase shift layer is lost
It carves and patterns, to produce phase-shift mask.It is alternately carried out film forming and patterning if so, then the shipping time between device
And processing latency will extend, production efficiency is remarkably decreased.Moreover, being covered across with the single of defined patterns of openings
Film can not continuously be etched phase shift layer and light shield layer, and need to form exposure mask (resist pattern) twice, cause to manufacture
Operation quantity increases.Accordingly, there exist cannot be with high production come the problem of manufacturing phase-shift mask.
Patent document 1: Japanese Unexamined Patent Publication 2011-13283 bulletin
Patent document 2: Japanese Unexamined Patent Publication 2006-78953 bulletin
In view of this, consider one kind on transparent substrate surface by phase shift layer, etch stop layer and light shield layer according to this
The phase-shift mask that sequence is configured.If such structure, when with photoetching process to manufacture phase-shift mask, can obtain in shading
The opening width for the pattern that layer the is formed edge enhancement type phase-shift mask wider than the opening width of phase-shift pattern, that is, work as vertical view
The edge enhancement type phase-shift mask that phase-shift pattern exposes from light-shielding pattern when observing phase-shift mask.
However, there are the following problems: in the area of the pattern as edge enhancement type phase-shift mask, though preferably as described above
The wide cut shape that phase-shift pattern exposes from light-shielding pattern, even if but due in the original alignment mark that must be same of plan view shape
Equal parts, opening shape (width dimensions) is also different with level, thus undesirable.
Summary of the invention
Mode according to the present invention be to solve the above-mentioned problems and propose, and it is an object of the present invention to provide it is a kind of be suitable for
In phase-shift mask of the high production to manufacture edge enhancement type phase-shift mask, phase-shift pattern in area of the pattern is formed simultaneously from screening
The plan view shape of the phase shift layer in wide cut shape and lightproof area, etch stop layer and the light shield layer that expose in light pattern is equal
Structure, so as to produce can be realized fine processing phase-shift mask method.
(1) phase-shift mask of a mode according to the present invention is characterised by comprising: transparent substrate；Phase shift layer, shape
At in the surface of the transparent substrate, using Cr as main component；Etch stop layer is formed in that side for leaving the transparent substrate
The phase shift layer surface, based at least one metal for being selected from Ni, Co, Fe, Ti, Si, Al, Nb, Mo, W and Hf
Want ingredient；And light shield layer, be formed on the etch stop layer for that side for leaving the phase shift layer, with Cr be mainly at
Point, the phase-shift mask includes phase shifting region, and the opening width of the light-shielding pattern formed on the light shield layer is set to compare
The opening width of the phase-shift pattern formed on the phase shift layer is wide；And lightproof area, formed on the phase shift layer described in
The opening width of phase-shift pattern and the opening width of the light-shielding pattern formed on the light shield layer are set
To be equal, in phase shifting region and lightproof area, the opening width of etch-stop pattern is set to the opening with light-shielding pattern
It is of same size.
(2) manufacturing method of the phase-shift mask of a mode according to the present invention, for manufacturing phase-shift mask, the phase
Moving exposure mask includes: transparent substrate；Phase shift layer is formed in the surface of the transparent substrate, using Cr as main component；Etch stop layer,
It is formed in the phase shift layer surface for that side for leaving the transparent substrate, with from Ni, Co, Fe, Ti, Si, Al, Nb, Mo, W
And at least one metal selected in Hf is main component；And light shield layer, it is formed in that side for leaving the phase shift layer
The etch stop layer on, using Cr as main component, the phase-shift mask includes phase shifting region, the shape on the light shield layer
At light-shielding pattern opening width be set to the phase-shift pattern than being formed on the phase shift layer opening width it is wide；And screening
Light region, the opening width of the phase-shift pattern formed on the phase shift layer and the institute formed on the light shield layer
The opening width for stating light-shielding pattern is set to equal, and the manufacturing method of the phase-shift mask is characterized in that, comprising:
The process of the phase shift layer, the etch stop layer and the light shield layer is formed on the transparent substrate；In the light shield layer
It is upper to form the process with the first exposure mask of defined patterns of openings；The first exposure mask across the formation is successively to the light shield layer
The process to form light-shielding pattern and etch-stop pattern is etched with the etch stop layer；Across first exposure mask pair
The process that the phase shift layer is etched to form phase-shift pattern；Second exposure mask with defined patterns of openings is formed, so that
The light-shielding pattern surface and the light-shielding pattern for being exposed to pattern openings are capped, and make the institute for being exposed to the pattern openings
It states etch-stop pattern and the phase-shift pattern is uncovered in the lightproof area and is capped in the phase shifting region
Process；The work that successively light-shielding pattern and the etch-stop pattern are etched across the second exposure mask of the formation
Sequence；And after removal second exposure mask, process that further the etch-stop pattern is etched.
(3) in the mode of above-mentioned (2), the etching containing nitric acid can be used in the etching of the etch stop layer
Liquid.
According to the mode of above-mentioned (1), by including: transparent substrate；Phase shift layer is formed in the surface of the transparent substrate, with
Cr is main component；Etch stop layer is formed in the phase shift layer surface for that side for leaving the transparent substrate, with from
At least one metal selected in Ni, Co, Fe, Ti, Si, Al, Nb, Mo, W and Hf is main component；And light shield layer, it is formed
In on the etch stop layer for that side for leaving the phase shift layer, using Cr as main component, and phase shifting region is included,
The opening width of the light-shielding pattern formed on the light shield layer is set to than the phase-shift pattern that is formed on the phase shift layer
Opening width is wide；And lightproof area, the opening width of the phase-shift pattern formed on the phase shift layer with described
The opening width of the light-shielding pattern formed on light shield layer be set to it is equal, thus in edge enhancement type phase-shift mask
In, in lightproof area, keep the opening width of phase-shift pattern, etch-stop pattern and light-shielding pattern equal, to maintain to be aligned
The accuracy of label, and the edge enhancement type phase-shift mask for coping with High precision can be produced with high production.
In addition, in the present invention, it is so-called using Cr as main component, refer to by the oxide, nitride, carbon from Cr and Cr
Any one selected in compound, nitrogen oxide, carbonization nitride and oxidation carbonization nitride is constituted.
According to the mode of above-mentioned (2), a method of for manufacturing phase-shift mask, the phase-shift mask includes: transparent base
Plate；Phase shift layer is formed in the surface of the transparent substrate, using Cr as main component；Etch stop layer, be formed in leave it is described transparent
The phase shift layer surface of that side of substrate, to be selected at least from Ni, Co, Fe, Ti, Si, Al, Nb, Mo, W and Hf
A kind of metal is main component；And light shield layer, it is formed on the etch stop layer for that side for leaving the phase shift layer,
Using Cr as main component, the phase-shift mask includes phase shifting region, and the opening of the light-shielding pattern formed on the light shield layer is wide
The opening width that degree is set to the phase-shift pattern than being formed on the phase shift layer is wide；And lightproof area, in the phase shift layer
The opening width of the phase-shift pattern of upper formation is opened with described in the light-shielding pattern formed on the light shield layer
Mouth width degree be set to it is equal, the method by include is formed on the transparent substrate phase shift layer, the etching end
The only process of layer and the light shield layer；The work with the first exposure mask of defined patterns of openings is formed on the light shield layer
Sequence；The first exposure mask across the formation is successively etched to form light-shielding pattern the light shield layer and the etch stop layer
With the process of etch-stop pattern；The phase shift layer is etched across first exposure mask to form the work of phase-shift pattern
Sequence；Second exposure mask with defined patterns of openings is formed, so as to the light-shielding pattern surface and be exposed to the screenings of pattern openings
Light pattern is capped, and makes the etch-stop pattern for being exposed to the pattern openings and the phase-shift pattern in the screening
The process for being uncovered in light region and being capped in the phase shifting region；The second exposure mask across the formation is successively to described
The process that light-shielding pattern and the etch-stop pattern are etched；And after removal second exposure mask, further to described
The process that etch-stop pattern is etched, in lightproof area, make phase shift figure in edge enhancement type phase-shift mask
The opening width of case, etch-stop pattern and light-shielding pattern is equal, to maintain the accuracy of alignment mark, and can be with height
Production copes with the edge enhancement type phase-shift mask of High precision to produce.
In the case where above-mentioned (3), use it can contain in the etching of the etch stop layer (etch-stop pattern)
The etching solution of nitric acid.
In phase shifting region, resist pattern (the first exposure mask) is formed on the light shield layer of phase-shift mask blank using as tool
There is the single exposure mask of defined patterns of openings, by being etched across the resist pattern to light shield layer, to form regulation
The light-shielding pattern of width.
In turn, by being etched across above-mentioned resist pattern to etch stop layer, to form etch-stop pattern.
At this point, the side of light-shielding pattern is exposed, but since light-shielding pattern is made of because without quilt the material different from etch-stop pattern
Etching, light-shielding pattern and etch-stop pattern become same widths.
Then, by being etched across above-mentioned resist pattern to phase shift layer, to be formed and etch-stop pattern phase
With the phase-shift pattern of width.At this point, since the light-shielding pattern being made of Cr based material identical with phase-shift pattern is also etched, because
The opening width of this light-shielding pattern becomes wider than the width of phase-shift pattern.By above-mentioned operation, the opening width of light-shielding pattern becomes
It obtains wider than the opening width of phase-shift pattern and etch-stop pattern.
In lightproof area, it is used in the same manner the first exposure mask, so that the opening width of light-shielding pattern becomes to compare phase-shift pattern
Opening width it is wide.Then, second exposure mask with defined patterns of openings is formed, so as to shading layer surface and be exposed to pattern
The light shield layer (side) of opening is capped, and makes the etch stop layer for being exposed to pattern openings and phase shift layer (phase-shift pattern) no
It is capped.
At this point, in phase shifting region, differently with lightproof area, light-shielding pattern surface and the shading for being exposed to pattern openings
The side of pattern, etch-stop pattern and phase-shift pattern is all covered by the second exposure mask.It is, being formed has than shading figure
Second exposure mask of the narrower defined width of the opening width of case, etch-stop pattern and phase-shift pattern.
Then, by being etched across side of the resist pattern to the phase-shift pattern for being exposed to pattern openings, from
And form the phase-shift pattern with opening width identical with the opening width of light-shielding pattern.At this point, being exposed to pattern openings
Light-shielding pattern is protected by the second exposure mask without being etched.Later, after removing the second exposure mask, finally to etch-stop pattern into one
Step is etched.At this point, being etched by the side only to etch-stop pattern, to be set to light-shielding pattern and erosion
It carves and terminates the side that pattern flushes.At this point, the side of phase-shift pattern and light-shielding pattern is exposed, but due to phase-shift pattern and shading figure
Case is constituted with the material different from etch-stop pattern because without being etched, phase-shift pattern, light-shielding pattern and etch-stop figure
Case becomes to flush.
Meanwhile in phase shifting region, etch-stop pattern is also etched.By above-mentioned operation, acquisition light-shielding pattern can be crossed
The edge enhancement type phase-shift mask wider than the opening width of phase-shift pattern with the opening width of etch-stop pattern.
In this way, only by the way that preformed phase-shift mask blank is patterned and can be produced in lightproof area
Phase-shift mask.Therefore, system can be more effectively carried out compared with alternately forming a film as the conventional example with patterned situation
It makes, moreover, can reduce manufacturing process's number compared to conventional example, it is thus possible to which phase-shift mask is manufactured with high production.
In the present invention, with Cr phase shift layer as main component by from the oxide of above-mentioned Cr, nitride, carbide, oxygen
Change any one selected in nitride, carbonization nitride and oxidation carbonization nitride to constitute, is set to sufficiently to send out
Wave the film thickness of phase shift effect.In order to this film thickness for giving full play to phase shift effect, erosion of the etching period relative to light shield layer
Time at quarter extends more than 1 times, but since the adhesion strength of each interlayer is sufficiently high, and it is substantially straight for being able to carry out line roughness
Linear and substantially vertical patterned section forms as good pattern for photomask.
In addition, by using the film containing Ni as etch stop layer, so as to sufficiently improve and the screening containing Cr
The adhesion strength of light film and the phase shift layer containing Cr.Thus, with wet etching liquid come to light shield layer, etch stop layer and phase
When shifting layer is etched, etching solution will not be from the interface and etch stop layer of light shield layer and etch stop layer and the boundary of phase shift layer
Face is penetrated into, therefore can be improved the CD precision for being formed by light-shielding pattern, phase-shift pattern, and can make the cross sectional shape of film at
For subvertical shape good for photomask.
According to the method for the present invention, it is being suitble to manufacture the phase shift of edge enhancement type phase-shift mask with high production
In exposure mask, the phase-shift pattern in area of the pattern is formed from the phase shift in the wide cut shape and lightproof area exposed in light-shielding pattern
The equal structure of the plan view shape of pattern, etch-stop pattern and light-shielding pattern, so as to produce the exposure mask of fine.
Detailed description of the invention
Fig. 1 is the process being illustrated to the manufacturing method of phase-shift mask involved in first embodiment of the invention
Figure.
Fig. 2 is the process being illustrated to the manufacturing method of phase-shift mask involved in first embodiment of the invention
Figure.
Specific embodiment
< first embodiment >
In the following, being illustrated based on an embodiment of the attached drawing to the manufacturing method of phase-shift mask according to the present invention.
Fig. 1 and Fig. 2 is the process chart for schematically showing the manufacturing method of phase-shift mask involved in present embodiment,
In figure, MB is phase-shift mask blank.
As shown in (a) of Fig. 1, phase-shift mask blank MB of the invention is formed by transparent substrate S, on transparent substrate S
Phase shift layer 11, the etch stop layer 12 formed on phase shift layer 11 and the light shield layer formed on the etch stop layer 12
13 are constituted.
As transparent substrate S, using excellent material in terms of the transparency and optical isotropy, it is, for example, possible to use
Quartz glass substrate or glass substrate.The size of transparent substrate S is simultaneously not particularly restricted, is exposed according to the exposure mask is used
Substrate (such as FPD substrate, semiconductor substrate) and it is suitably selected.In the present embodiment, it can be applied to diameter dimension
The substrate of 100mm or so or from one side for 50~100mm or so to while be 300mm or more rectangular substrate may be used also in turn
To use longitudinal 450mm, transverse direction 550mm, the quartz base plate of thickness 8mm or maximum side size 1000mm or more and thickness 10mm
Above substrate.
Furthermore, it is possible to be ground by the surface to transparent substrate S, to reduce the flatness of transparent substrate S.It is transparent
The flatness of substrate S for example can be set to 20 μm or less.Accordingly, the depth of focus of exposure mask can deepen, so as to fine and
Larger contribution is made in high-precision pattern formation.In turn, preferably as low as 10 μm or less of flatness.
Phase shift layer 11 and light shield layer 13 are using Cr as main component, specifically, can be by the oxygen from Cr simple substance and Cr
One kind for selecting is constituted in compound, nitride, carbide, nitrogen oxide, carbonization nitride and oxidation carbonization nitride,
Further, it is also possible to be constituted by being laminated select among these two or more.
Phase shift layer 11 is with any one light for 300nm or more and in 500nm wavelength region below (for example, wavelength
The i line of 365nm) there can be substantially 180 ° of the thickness (for example, 90~170nm) of phase difference to be formed.Light shield layer 13 is with energy
Obtain the thickness (for example, 80nm~200nm) of defined optical characteristics enough to be formed.As etch stop layer 12, can be used
With at least one metal material as main component selected from Ni, Co, Fe, Ti, Si, Al, Nb, Mo, W and Hf, example
Such as, Ni-Ti-Nb-Mo film can be used.Above-mentioned phase shift layer 11, etch stop layer 12 and light shield layer 13 can be for example, by splashing
Method, e-beam evaporation, laser ablation method, ALD method etc. are penetrated to form a film.
The phase-shift mask M of present embodiment has the phase shift layer (phase-shift pattern) 11 for the phase difference that can have 180 °, and
Opening width d2 with the light-shielding pattern 13b formed on light shield layer 13 is set to the phase than being formed on the phase shift layer 11
Move the opening of the phase shifting region PSA and the phase-shift pattern 11b formed on phase shift layer 11 of the opening width d1 wide of pattern 11a
Width d5 is set to equal lightproof area MSA with the opening width d5 of the light-shielding pattern 13b formed on light shield layer 13.
Alignment mark AM for example can be set in lightproof area MSA, lightproof area MSA can be to surround when overlook view
Mode around the PSA of phase shifting region is arranged around the peripheral part of transparent substrate S.
It include g line (436nm), h line (405nm) by the way that the light of above-mentioned wavelength region to be especially according to phase-shift mask M
And the composite wavelength including i line (365nm) is used as exposure light, it is the smallest so as to form luminous intensity because of phasing back effect
Region, so that exposing patterns are more distinct.According to this phase shift effect, pattern accuracy can be greatly improved, is realized fine and high
The pattern of precision is formed.Phase shift layer can be formed with oxidation nitridation chromium based material, and the thickness of above-mentioned phase shift layer can be set to needle
There is the thickness of substantially 180 ° of phase differences to i line.It in turn, can also be can there are substantially 180 ° of phase differences for h line or g line
Thickness form above-mentioned phase shift layer.Here, so-called " substantially 180 ° " refer to 180 ° or close to 180 °, for example, 180 ° ± 10 °
Below.According to the phase-shift mask, the pattern accuracy based on phase shift effect can be realized by using the light of above-mentioned wavelength region
It improves, to realize that fine and high-precision pattern is formed.Hereby it is possible to produce the flat-panel monitor of high image quality.
The phase-shift mask of present embodiment is configured to the patterning exposure mask for example for FPD glass substrate.Such as
It is described afterwards, in order to carry out the patterning of the glass substrate using the exposure mask, using the compound of i line, h line and g line in exposure light
Wavelength.
As shown in (a) of Fig. 1, the phase-shift mask blank MB of present embodiment is by using DC sputtering method in glass substrate
S it is upper to using Cr phase shift layer 11 as main component, using Ni etch stop layer 12 as main component and using Cr as main component
Light shield layer 13 successively formed a film and produced.Hereinafter, for producing phase-shift mask M from above-mentioned phase-shift mask blank MB
Phase-shift mask manufacturing method be illustrated.
Then, as shown in (b) of Fig. 1, light is formed on the light shield layer 13 of the top layer as phase-shift mask blank MB
Cause resist layer PR1a.Photoresist layer PR1a can be positive flap-type and be also possible to egative film type.As photoresist layer
Using liquid resist, but dry film photoresist also can be used in PR1a.
Then, as shown in (c) of Fig. 1, (d), by the way that photoresist layer PR1a is exposed and is developed, to remove
Region PR1b and on light shield layer 13 formed resist pattern RP1.Etching mask of the resist pattern RP1 as light shield layer 13
It functions, proper shape is determined according to the etched pattern of light shield layer 13.As an example, in phase shifting region
In PSA, it is set with the shape of the opening width d1 equal with the opening width size d1 for the phase-shift pattern to be formed.
Then, as shown in (e) of Fig. 1, light shield layer 13 is carried out using the first etching solution across resist pattern RP1
Wet etching.As the first etching solution, the erosion containing ammonium ceric nitrate (the 2nd ア Application モ ニ ウ system of nitric acid セ リ ウ system) can be used
Liquid is carved, for example, it is preferable to use the ammonium ceric nitrate containing the acid such as nitric acid or perchloric acid.Here, since etch stop layer 12 is for
One etching solution has height endurability, therefore only light shield layer 13 is patterned and forms light-shielding pattern 13a.Light-shielding pattern 13a is set
For the shape with the opening width d1 equal with resist pattern RP1.
Then, as shown in (f) of Fig. 1, across above-mentioned resist pattern RP using the second etching solution come to etch stop layer
12 carry out wet etching.As the second etching solution, can be properly used will be from acetic acid, perchloric acid, aquae hydrogenii dioxidi and hydrochloric acid
That selects at least one is added to the liquid obtained after nitric acid.Here, since light shield layer 13 and phase shift layer 11 are for the second erosion
Carving liquid has height endurability, therefore only etch stop layer 12 is patterned and forms etch-stop pattern 12a.Etch-stop pattern
12a is set as the shape with the opening width d1 equal with the opening width size d1 of light-shielding pattern 13a and resist pattern RP1
Shape.
Then, as shown in (g) of Fig. 1, across resist pattern RP1, that is, in the shape for not removing resist pattern RP1
Under state, wet etching is carried out to phase shift layer 11 using the first etching solution.Here, light-shielding pattern 13a is with identical with phase shift layer 11
Cr based material is constituted, and since the side of light-shielding pattern 13a is exposed, phase shift layer 11 is patterned and forms phase-shift pattern
11a.Phase-shift pattern 11a is set as the shape with opening width size d1.Meanwhile light-shielding pattern 13a is also further across side
Facet etch and the light-shielding pattern for forming the shape with opening width size d1 than phase-shift pattern 11a bigger opening width d2
13b.At this point, etch-stop pattern 12a and phase-shift pattern 11a, which becomes, has the opening width d1 equal with resist pattern RP1
Shape.
Then, as shown in (h) of Fig. 2, resist pattern RP1 is removed.In the removal of resist pattern RP1, due to can
To use well known anticorrosive additive stripping liquid controlling, therefore detailed description is omitted herein.
Up to the present, it is illustrated for the size in the PSA of phase shifting region, and in lightproof area MSA, for example,
Etch-stop pattern 12a and phase-shift pattern 11a is set as the shape with the opening width d3 equal with resist pattern RP1,
Light-shielding pattern 13b is set as the shape with the opening width size d3 than phase-shift pattern 11a bigger opening width d5.
In addition, in the opening for the near border for being located at phase shifting region PSA and lightproof area MSA, for example, etch-stop figure
Case 12a and phase-shift pattern 11a is set as the shape with the opening width d6 equal with resist pattern RP1, light-shielding pattern 13b
It is set as the shape with the opening width size d6 than phase-shift pattern 11a bigger opening width d4.
Then, as shown in (j) of Fig. 2, entire surface on glass substrate S forms photoresist layer PR2a.At this point,
Photoresist layer PR2a is arranged to the entire surface on cover glass substrate S, also includes passing through light-shielding pattern 13b, phase shift figure
Case 11a, etch-stop pattern 12a and the inside of opening formed.
Then, as shown in (k) of Fig. 2, (m), by the way that photoresist layer PR2a is exposed and is developed, to remove
Region PR2b and form resist pattern RP2.At this point, resist pattern RP2 is arranged to the opening figure on cover glass substrate S
The entire surface of case also includes in the opening formed by light-shielding pattern 13b, phase-shift pattern 11a, etch-stop pattern 12a
Portion.Resist pattern RP2 is set as the pattern form similar with the patterns of openings on glass substrate S, that is, with resist
Pattern RP1 similar flat shape, and it is different to be formed its opening width size.
Specifically, in phase shifting region PSA and opening positioned at phase shifting region PSA and the near border of lightproof area MSA
In mouthful, resist pattern RP2 is set as with the smaller opening width of opening width size d1, d6 than resist pattern RP1
The shape of d10, d7.It is, for resist pattern RP2, pattern is improved to set position of the luminous intensity as zero at these
Change in the pattern part that precision is the starting point, width dimensions are set to covering by above-mentioned light-shielding pattern 13b, phase-shift pattern
The side inside patterns of openings formed after 11a, etch-stop pattern 12a lamination.
In addition, resist pattern RP2 is set as with the opening width with resist pattern RP1 in lightproof area MSA
The shape of size d3 equal opening width, width dimensions are set in the side of open interior formed after lamination
It only covers the side of light-shielding pattern 13b and exposes the side of phase-shift pattern 11a, etch-stop pattern 12a.
Then, as shown in (n) of Fig. 2, across resist pattern RP2, that is, in the shape covered by resist pattern RP2
Under state, wet etching is carried out to phase-shift pattern 11a using the first etching solution.Here, no matter light-shielding pattern 13b is due in phase shift
Which all covered by resist pattern RP2 in region PSA and lightproof area MSA, because without being etched.
Meanwhile in the PSA of phase shifting region, phase-shift pattern 11a by resist pattern RP2 due to being covered, because without being etched.
In addition, the phase-shift pattern 11a being made of Cr based material forms phase by side etching in lightproof area MSA
Move pattern 11b.Phase-shift pattern 11b is set as the shape with opening width size d5, d9.Meanwhile light-shielding pattern 13b is not eclipsed
It carves.As a result, it is possible to the opening width of phase-shift pattern 11b is dimensioned to opening width d5 identical with light-shielding pattern 13b.
In addition, etch-stop pattern 12a maintains the shape with opening width d3, d6 equal with before this process.
Then, as shown in (p) of Fig. 2, resist pattern RP2 is removed.Resist pattern RP2 can be with resist pattern
RP1 is similarly removed.
Then, as shown in (q) of Fig. 2, further to carry out etch-stop pattern 12a using above-mentioned second etching solution wet
Formula etching.Accordingly, the opening width of etch-stop pattern 12b is set as opening width d2, d4 and d5 phase with light-shielding pattern 13b
Together.
As a result, as shown in (q) of Fig. 2, light-shielding pattern 13b (and etch-stop pattern can be obtained in the PSA of phase shifting region
The edge enhancement type phase-shift mask M of opening width d1 wide of opening width d2 12b) than phase-shift pattern 11b.
In phase-shift mask M, in lightproof area MSA, phase-shift pattern 11b, light-shielding pattern 13b, etch-stop pattern 12b
Opening width d5 it is equal, it is, as alignment mark AM patterns of openings in phase-shift pattern 11b, light-shielding pattern 13b,
The side of etch-stop pattern 12b flushes, and becomes the shape roughly equal with the exposure directions of exposure-processed.
Moreover, can obtain in the opening of near border for being located at phase shifting region PS and lightproof area MSA, such as shading
The edge enhancement type of opening width d9 wide of the opening width d4 than phase-shift pattern 11b of pattern 13b (and etch-stop pattern 12b)
Phase-shift mask M.Meanwhile phase-shift pattern 11b, light-shielding pattern 13b, etch-stop figure in the patterns of openings of the side lightproof area MSA
The side of case 12b flushes, and becomes the shape roughly equal with the exposure directions of exposure-processed.
In addition, being exposed to the width (d2-d1) of the phase-shift pattern 11a on the outside of light-shielding pattern 13b in the PSA of phase shifting region
The etching speed of light-shielding pattern 13b when by carrying out wet etching to phase shift layer 11 determines.Here, the erosion of light-shielding pattern 13a
Carving speed will receive the influence of composition and etch stop layer 12 and the interface state of light shield layer 13 of light shield layer 13.For example,
By with chromium layer as main component and with this two layers film of chromium oxide layer as main component come when being constituted light shield layer 13, if made
It then can be improved etching speed with the ratio raising of the chromium component of chromium layer as main component, on the other hand, if making chromium component
Ratio reduction then can reduce etching speed.As the etch quantity of light-shielding pattern 13a, such as can be in 200nm~1000nm
In the range of set.
According to above embodiment, on transparent substrate S, phase shift layer 11, etch stop layer 12 and light shield layer 13 are pressed
Lamination is carried out according to this sequence and constitutes phase-shift mask blank MB.Pass through the shape on the light shield layer 13 of phase-shift mask blank MB
Wet etching is carried out to each layer at resist pattern RP1, RP2, and using resist pattern RP1, RP2, so as to make
Produce the high edge enhancement type phase-shift mask M of the position accuracy of alignment mark AM.Therefore, with repeat form a film and etch
Conventional example is compared, can reduce manufacturing process's number, and can be improved production efficiency, therefore can be produced with high production
Fine and high visual phase-shift mask M.
In addition, phase shift layer 11 is by from the oxide of Cr, nitride, carbide, nitrogen oxide, carbonization nitride and oxygen
Change any one selected in carbonization nitride to constitute, there is the film thickness for giving full play to phase shift effect.In order to this
The film thickness of phase shift effect is given full play to, etching period is extended relative to the etching period of light shield layer 13 more than 1 times, but due to each
The adhesion strength of interlayer is sufficiently high, therefore being able to carry out line roughness is substantially linear and the substantially vertical conduct of patterned section
Good pattern is formed for photomask.
In addition, by using the film containing Ni as etch stop layer 12, so as to sufficiently improve and containing Cr's
The adhesion strength of light shield layer 13 and the phase shift layer 11 containing Cr.
Thus, when with wet etching liquid to be etched to light shield layer 13, etch stop layer 12 and phase shift layer 11, erosion
Carving liquid will not penetrate into from the interface and etch stop layer 12 of light shield layer 13 and etch stop layer 12 and the interface of phase shift layer 11, because
This can be improved the CD precision for being formed by light-shielding pattern 13b, phase-shift pattern 11a, and the cross sectional shape of film can be made to become
The good subvertical shape for photomask.
In order to confirm said effect, following experiment has been carried out.That is, on glass substrate S, by sputtering method, according to 120nm
Thickness form a film to the oxidation nitridation carbonized film of the chromium as phase shift layer 11, according to the thickness of 30nm to as etch-stop
The Ni-Ti-Nb-Mo film of layer 12 forms a film, and the aggregate thickness according to 100nm is to by main component being chromium as light shield layer 13
Layer and main component be that the film of this two layers of layer composition of chromium oxide forms a film, to obtain phase-shift mask blank MB.
Resist pattern RP1 is formed on phase-shift mask blank MB, uses ammonium ceric nitrate across resist pattern RP1
Light shield layer 13 is etched with the mixing etching solution of perchloric acid and forms light-shielding pattern 13a, and then uses nitric acid and perchloric acid
Mixing etching solution etch stop layer 12 is etched and forms etch-stop pattern 12a.Then, using ammonium ceric nitrate with
The mixing etching solution of perchloric acid is etched phase shift layer 11 and forms phase-shift pattern 11a.
Then, resist pattern RP2 is formed, the mixing of ammonium ceric nitrate and perchloric acid is used across resist pattern RP2
Etching solution carries out side etching to phase-shift pattern 11a and forms phase-shift pattern 11b.Then, resist pattern RP2 is removed, is connect
, etch-stop pattern 12a is etched using the mixing etching solution of nitric acid and perchloric acid and forms etch-stop pattern
12b, to obtain edge enhancement type phase-shift mask M.
Using the phase-shift mask M so obtained, exposed using the exposure light of the composite wavelength of g line, h line and i line
Light measures the line width of the pattern after exposure, the offset relative to target line width (2.5 μm) has been found out, as a result, really
It accepts and is able to suppress to 10% or so.Simultaneously, it is thus identified that the profile of alignment mark AM is visual good.Accordingly, having distinguished can be with
It will be used with the phase-shift mask M that high production manufactures for FPD.
Embodiments of the present invention are illustrated above, but the present invention is not limited to this, is not departing from invention
In the range of objective, it can be suitably changed.
Symbol description
MB ... phase-shift mask blank, S ... glass substrate (transparent substrate), 11 ... phase shift layers, 11a ... phase-shift pattern, 12 ...
Etch stop layer, 12a, 12b ... etch-stop pattern, 13 ... light shield layers, 13a, 13b ... light-shielding pattern.
Claims (2)
1. a kind of manufacturing method of phase-shift mask, for manufacturing phase-shift mask, the phase-shift mask includes:
Transparent substrate；
Phase shift layer is formed in the surface of the transparent substrate, using Cr as main component；
Etch stop layer is formed in the phase shift layer surface for that side for leaving the transparent substrate, with from Ni, Co, Fe,
At least one metal selected in Ti, Si, Al, Nb, Mo, W and Hf is main component；And
Light shield layer is formed on the etch stop layer for that side for leaving the phase shift layer, using Cr as main component,
The phase-shift mask includes phase shifting region, and the opening width of the light-shielding pattern formed on the light shield layer is set to
The opening width of phase-shift pattern than being formed on the phase shift layer is wide；And lightproof area, the institute formed on the phase shift layer
The opening width of the opening width and the light-shielding pattern formed on the light shield layer of stating phase-shift pattern is set
Be set to it is equal,
The manufacturing method of the phase-shift mask is characterized in that, comprising:
The process of the phase shift layer, the etch stop layer and the light shield layer is formed on the transparent substrate；
The process with the first exposure mask of defined patterns of openings is formed on the light shield layer；
The first exposure mask across the formation is successively etched to form shading figure the light shield layer and the etch stop layer
The process of case and etch-stop pattern；
The process to form phase-shift pattern is etched to the phase shift layer across first exposure mask；
Second exposure mask with defined patterns of openings is formed, so as to the light-shielding pattern surface and be exposed to the screenings of pattern openings
Light pattern is capped, and makes the etch-stop pattern for being exposed to the pattern openings and the phase-shift pattern in the screening
The process for being uncovered in light region and being capped in the phase shifting region；
The process that successively light-shielding pattern and the etch-stop pattern are etched across the second exposure mask of the formation；With
And
After removing second exposure mask, process that further the etch-stop pattern is etched.
2. the manufacturing method of phase-shift mask according to claim 1, which is characterized in that in the etching of the etch stop layer
Etching solution of the middle use containing nitric acid.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012-285846 | 2012-12-27 | ||
| JP2012285846 | 2012-12-27 | ||
| PCT/JP2013/084089 WO2014103875A1 (en) | 2012-12-27 | 2013-12-19 | Phase shift mask and method for producing same |
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| Publication Number | Publication Date |
|---|---|
| CN104718496A CN104718496A (en) | 2015-06-17 |
| CN104718496B true CN104718496B (en) | 2019-06-28 |
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| CN201380052684.3A Active CN104718496B (en) | 2012-12-27 | 2013-12-19 | The manufacturing method of phase-shift mask |
Country Status (5)
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|---|---|
| JP (1) | JP5865520B2 (en) |
| KR (1) | KR101785177B1 (en) |
| CN (1) | CN104718496B (en) |
| TW (1) | TWI592739B (en) |
| WO (1) | WO2014103875A1 (en) |
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| WO2001001195A1 (en) * | 1999-06-29 | 2001-01-04 | U.S. Precision Lens Incorporated | Optical systems for projection displays |
| JP6391495B2 (en) * | 2015-02-23 | 2018-09-19 | Hoya株式会社 | Photomask, photomask set, photomask manufacturing method, and display device manufacturing method |
| JP6456748B2 (en) * | 2015-03-28 | 2019-01-23 | Hoya株式会社 | Photomask manufacturing method, photomask and flat panel display manufacturing method |
| EP3410215B1 (en) * | 2016-01-27 | 2020-06-17 | LG Chem, Ltd. | Film mask, method for manufacturing same, and method for forming pattern using film mask and pattern formed thereby |
| JP6756796B2 (en) * | 2018-10-09 | 2020-09-16 | アルバック成膜株式会社 | Mask blanks, halftone masks, manufacturing method |
Citations (3)
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| CN1603948A (en) * | 2003-09-05 | 2005-04-06 | 肖特股份有限公司 | Attenuating phase shift mask blank and photomask |
| CN1837956A (en) * | 2005-03-22 | 2006-09-27 | Hoya株式会社 | Gray tone mask and thin film transistor substrate manufacturing method |
| CN101842744A (en) * | 2007-11-01 | 2010-09-22 | 爱发科成膜株式会社 | Half-tone mask, half-tone mask blank and method for manufacturing half-tone mask |
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| JPH0450942A (en) * | 1990-06-15 | 1992-02-19 | Fujitsu Ltd | Reticle and its manufacturing method |
| JP3209257B2 (en) * | 1995-04-21 | 2001-09-17 | 凸版印刷株式会社 | Phase shift mask and method of manufacturing the same |
| JPH08334885A (en) * | 1995-06-02 | 1996-12-17 | Toppan Printing Co Ltd | Halftone type phase shift mask and its production |
| JP3244107B2 (en) * | 1995-06-02 | 2002-01-07 | 凸版印刷株式会社 | Halftone phase shift mask and method of manufacturing the same |
| KR100429860B1 (en) * | 1997-05-27 | 2004-06-16 | 삼성전자주식회사 | Alternating Phase Inversion Mask and Manufacturing Method Thereof |
| JP2005208660A (en) * | 2004-01-22 | 2005-08-04 | Schott Ag | Phase shift type mask blank of super-high transmission ratio |
| JP2005257962A (en) * | 2004-03-11 | 2005-09-22 | Semiconductor Leading Edge Technologies Inc | Phase shift mask and method for manufacturing phase shift mask |
| JP4490980B2 (en) * | 2007-02-16 | 2010-06-30 | クリーンサアフェイス技術株式会社 | Halftone blanks |
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2013
- 2013-12-19 KR KR1020157010520A patent/KR101785177B1/en active Active
- 2013-12-19 WO PCT/JP2013/084089 patent/WO2014103875A1/en active Application Filing
- 2013-12-19 CN CN201380052684.3A patent/CN104718496B/en active Active
- 2013-12-19 JP JP2014554380A patent/JP5865520B2/en active Active
- 2013-12-25 TW TW102148235A patent/TWI592739B/en active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1603948A (en) * | 2003-09-05 | 2005-04-06 | 肖特股份有限公司 | Attenuating phase shift mask blank and photomask |
| CN1837956A (en) * | 2005-03-22 | 2006-09-27 | Hoya株式会社 | Gray tone mask and thin film transistor substrate manufacturing method |
| CN101842744A (en) * | 2007-11-01 | 2010-09-22 | 爱发科成膜株式会社 | Half-tone mask, half-tone mask blank and method for manufacturing half-tone mask |
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| KR20150063093A (en) | 2015-06-08 |
| JP5865520B2 (en) | 2016-02-17 |
| TWI592739B (en) | 2017-07-21 |
| JPWO2014103875A1 (en) | 2017-01-12 |
| WO2014103875A1 (en) | 2014-07-03 |
| CN104718496A (en) | 2015-06-17 |
| TW201432370A (en) | 2014-08-16 |
| KR101785177B1 (en) | 2017-11-06 |
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