WO2023008532A1 - ペリクル膜、ペリクル、ペリクル付き露光原版、露光方法、半導体の製造方法及び液晶表示板の製造方法 - Google Patents
ペリクル膜、ペリクル、ペリクル付き露光原版、露光方法、半導体の製造方法及び液晶表示板の製造方法 Download PDFInfo
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- WO2023008532A1 WO2023008532A1 PCT/JP2022/029162 JP2022029162W WO2023008532A1 WO 2023008532 A1 WO2023008532 A1 WO 2023008532A1 JP 2022029162 W JP2022029162 W JP 2022029162W WO 2023008532 A1 WO2023008532 A1 WO 2023008532A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- pellicle
- film
- exposure
- bnnt
- original plate
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 36
- 238000004519 manufacturing process Methods 0.000 title claims description 20
- 239000004065 semiconductor Substances 0.000 title claims description 11
- 239000004973 liquid crystal related substance Substances 0.000 title claims description 10
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000000853 adhesive Substances 0.000 claims abstract description 16
- 230000001070 adhesive effect Effects 0.000 claims abstract description 16
- 238000000206 photolithography Methods 0.000 claims abstract description 7
- 239000012528 membrane Substances 0.000 claims description 15
- 239000000758 substrate Substances 0.000 claims description 14
- 238000002834 transmittance Methods 0.000 claims description 12
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 abstract description 2
- 230000008569 process Effects 0.000 description 11
- 239000000463 material Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 239000012790 adhesive layer Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 230000001681 protective effect Effects 0.000 description 5
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 238000001459 lithography Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- -1 polyethylene terephthalate Polymers 0.000 description 4
- 238000000550 scanning electron microscopy energy dispersive X-ray spectroscopy Methods 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000002041 carbon nanotube Substances 0.000 description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 239000013464 silicone adhesive Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000003522 acrylic cement Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229910000085 borane Inorganic materials 0.000 description 2
- BGECDVWSWDRFSP-UHFFFAOYSA-N borazine Chemical compound B1NBNBN1 BGECDVWSWDRFSP-UHFFFAOYSA-N 0.000 description 2
- 239000002238 carbon nanotube film Substances 0.000 description 2
- KZPXREABEBSAQM-UHFFFAOYSA-N cyclopenta-1,3-diene;nickel(2+) Chemical compound [Ni+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KZPXREABEBSAQM-UHFFFAOYSA-N 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 230000017525 heat dissipation Effects 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910052580 B4C Inorganic materials 0.000 description 1
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 description 1
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- QDWJUBJKEHXSMT-UHFFFAOYSA-N boranylidynenickel Chemical compound [Ni]#B QDWJUBJKEHXSMT-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 229920002313 fluoropolymer Polymers 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
- 238000004050 hot filament vapor deposition Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910003465 moissanite Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001012 protector Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000003075 superhydrophobic effect Effects 0.000 description 1
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/064—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with boron
- C01B21/0648—After-treatment, e.g. grinding, purification
-
- 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
- G03F1/62—Pellicles, e.g. pellicle assemblies, e.g. having membrane on support frame; 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
- 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
- G03F7/20—Exposure; Apparatus therefor
-
- 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
- G03F7/70983—Optical system protection, e.g. pellicles or removable covers for protection of mask
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
- C01P2004/13—Nanotubes
Definitions
- the present invention relates to a pellicle film and a pellicle using the same, which is used as a lithography photomask dust protector for manufacturing semiconductor devices such as LSI and VLSI and liquid crystal displays.
- photolithography The development of exposure technology called photolithography has made it possible to increase the integration of semiconductor repair circuits.
- the photolithography process uses a photomask as an original for patterning, and the pattern on the photomask is transferred to the wafer. At this time, if impurities such as particles and foreign matter adhere to the photomask, the exposure light is absorbed or reflected by the impurities, damaging the transferred pattern. lead to decline.
- a method of attaching a pellicle to the photomask is used.
- the pellicle is generally placed above the surface of the photomask, and even if impurities adhere to the pellicle, the focal point is aligned with the pattern of the photomask during the photolithography process, so dust or foreign matter on the pellicle does not It is out of focus and not transferred to the pattern.
- circuit line widths have become finer, the size of impurities that can affect pattern damage has decreased, and the role of pellicles in protecting photomasks has become more important.
- the pellicle When the pellicle is composed of a single film, it is possible to easily secure the transmittance by applying a substance having a low extinction coefficient for extreme ultraviolet light of 13.5 nm. It is extremely difficult to ensure the properties.
- the pellicle film when the pellicle film is irradiated with EUV, part of the energy is absorbed by the pellicle film. Then, the EUV energy absorbed by the pellicle film is converted into heat through various relaxation processes. Therefore, the temperature of the pellicle film rises during EUV exposure. Therefore, the pellicle film is required to have high heat dissipation and heat resistance.
- Patent Document 1 describes a pellicle film made of single crystal silicon.
- this single crystal silicon film has a low heat dissipation property and a low melting point. Therefore, there is a problem that the pellicle film is easily damaged during EUV irradiation.
- Patent Document 2 describes a pellicle membrane made of graphene.
- Graphene is an aggregate of small crystals, which makes the pellicle membrane fragile and has insufficient durability. Moreover, even if a large number of such graphenes are laminated, it is difficult to ensure sufficient strength for the pellicle film.
- Patent Document 3 proposes a pellicle membrane made of carbon nanotubes. Carbon nanotube pellicle membranes are not resistant to hydrogen radicals generated during the EUV exposure process. The process was complicated.
- the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a pellicle film having high transmittance in EUV exposure, excellent heat resistance and durability, and hydrogen radical resistance, and a pellicle comprising the same. is to provide
- the present inventors have made intensive studies to solve the above problems, and found that by selecting boron nitride nanotubes (BNNT) as the material of the pellicle film for EUV exposure, the Furthermore, the inventors have found that the pellicle membrane is stable against hydrogen radicals without coating the surface of the pellicle membrane with a special material, leading to the present invention. .
- BNNT boron nitride nanotubes
- the present invention provides the following pellicle film, pellicle, exposure original plate with pellicle, exposure method, semiconductor manufacturing method, and liquid crystal display panel manufacturing method.
- a pellicle film comprising a film having boron nitride nanotubes (BNNT film).
- BNNT film boron nitride nanotubes
- 3. The pellicle film according to 1 or 2 above, wherein the ratio of the thickness of the BNNT film to the total thickness of the pellicle film is 90% or more. 4.
- the pellicle film according to any one of 1 to 3 above which has a transmittance of 80% or more for light having a wavelength of 13.5 nm. 5.
- the pellicle film according to any one of 1 to 4 above which is used for exposure to extreme ultraviolet (EUV) light using 13.5 nm wavelength as the main exposure wavelength.
- EUV extreme ultraviolet
- a pellicle for photolithography comprising a pellicle film and a pellicle frame, wherein the pellicle film is provided on one end surface of the pellicle frame via an adhesive, wherein the pellicle film is the pellicle film according to any one of 1 to 5 above.
- a pellicle-equipped exposure original plate comprising the pellicle described in 6 above mounted on an exposure original plate. 8. 8. The exposure original plate with a pellicle as described in 7 above, wherein the exposure original plate is an EUV exposure original plate. 9. 9. An exposure method comprising exposing using the pellicle-attached exposure original plate according to 8 above. 10. 8. A method for manufacturing a semiconductor, comprising a step of exposing a substrate in vacuum or under reduced pressure using the exposure original plate with a pellicle according to 7 above. 11. 8. A method for manufacturing a liquid crystal display panel, comprising a step of exposing a substrate in vacuum or under reduced pressure using the exposure original plate with a pellicle according to 7 above. 12. 8.
- a method for manufacturing a semiconductor comprising a step of subjecting a substrate to EUV exposure using the exposure original plate with a pellicle according to 8 above. 13.
- a method for manufacturing a liquid crystal display panel comprising a step of subjecting a substrate to EUV exposure using the exposure original plate with a pellicle according to the above item 7.
- the pellicle film of the present invention is a film made of boron nitride nanotubes (BNNT film).
- BNNT film a film having boron nitride nanotubes
- the BNNT film preferably has 90% by mass or more of boron nitride nanotubes, more preferably 95% by mass or more of boron nitride nanotubes, and particularly preferably has 98% by mass or more of boron nitride nanotubes.
- substantially composed of boron nitride nanotubes means that the components of the film excluding catalysts and impurity components are composed of boron nitride nanotubes. Further, within the range where the effects of the present invention can be utilized, it may be composited with various materials such as carbon nanotubes.
- BNNT film can refer to a connected arrangement of BNNTs, such as meshes, webs, grids, etc. formed from individual BNNTs or bundles of BNNTs.
- Individual BNNTs (single-walled BNNTs or multi-walled BNNTs, MWBNNTs) of a BNNT film can be aligned to form bundles. Such bundles of aligned BNNTs tend to form spontaneously during the fabrication of BNNT films.
- the BNNT bundles in the BNNT film or the BNNT bundles can be randomly arranged within the BNNT film.
- the BNNTs or BNNT bundles of the BNNT film may be arranged or aligned along a critical or principal direction, or along multiple principal directions.
- the BNNTs in the BNNT film can also be single-walled BNNTs (SWBNNTs) or multi-walled BNNTs (MWBNNTs).
- SWBNNTs single-walled BNNTs
- MWBNNTs multi-walled BNNTs
- the BNNT film may be formed by SWBNNTs or bundles of SWBNNTs, or even MWBNNTs or bundles of MWBNNTs.
- BNNTs can be synthesized using a floating catalytic CVD method.
- BNNT can be synthesized by reacting amine borane borazine (B 3 N 3 H 6 ) or decaborane B 10 H 14 with nickelocene in ammonia at 1200 to 1300°C.
- the synthesized BNNTs are deposited on a hydrophobic filter, but can aggregate together to form a film due to intermolecular forces (van der Waals forces) acting between the BNNTs.
- a second support different from the pellicle frame, is used to release the BNNT deposited on the filter and transfer the BNNT film from the support to the pellicle frame.
- a silicone-based pressure-sensitive adhesive e.g., "KE-101A/B” manufactured by Shin-Etsu Chemical Co., Ltd.
- a pellicle can be completed by attaching the upper end face side of the pellicle frame to the BNNT film attached to the support larger than the pellicle frame and removing the portion outside the pellicle frame.
- the boron powder is ball-milled, and then in the presence of a metal oxide catalyst such as Fe 2 O 3 , Ga 2 O 3 , MgO, or Li 2 O, or in the presence of metallic iron and nickel boride, BNNT can also be synthesized by thermal CVD reaction with ammonia at 1100°C.
- the synthesized BNNTs aggregate by mutual intermolecular force to form a film on the Si substrate.
- the BNNT film formed by this manufacturing method can also be finally transferred to the pellicle frame through the second support, as in the floating catalyst CVD method.
- BNNTs can also be prepared by various methods known in the art, including, but not limited to, arc discharge, laser vaporization, dispersion filtration, and the like.
- suitable BNNT films for use in embodiments of the present invention can be prepared as described in WO 2019/006549, "Methods for Preparing Films with Superhydrophobic Nano-Macroscale Patterns" It can be prepared and then made into a self-supporting film by transfer.
- the BNNT film in the present invention has high resistance to hydrogen radicals, it does not require a protective film or tube coating that is normally formed on a carbon nanotube film (CNT film).
- the BNNT film of the present invention may also be provided with such a protective film or coating, but in this case, these members can be provided in the necessary minimum. Therefore, the thickness of the BNNT film in the thickness of the pellicle film can be set to 90% or more, and the pellicle film substantially composed of only the BNNT film can function as a pellicle film for EUV exposure.
- the protective film is, for example, provided on one side or both sides of the BNNT film, and specifically includes SiO x (x ⁇ 2), Sia N b (a/ b is 0.7 to 1.5), SiON , Y2O3 , YN, Mo, Ru, Rb, Sr, Y, Zr, Nb, B4C , SiC and Rh.
- the coating for example, the material used for the protective film can be used.
- BNNT film when the surface of the BNNT film is observed with a scanning electron microscope (SEM)-energy dispersive X-ray (EDX) analyzer, among the observed elements, B element, N element and elements constituting the catalyst A BNNT film having a region occupying 90 mol % or more can be obtained.
- a BNNT film substantially composed of B element, N element, and elements constituting a catalyst can function as a pellicle film for EUV exposure.
- the elements constituting the catalyst may be removed by heat treatment, and in this case, the above proportions are the proportions occupied by the B element and the N element.
- the above observation by SEM-EDX can be determined by, for example, mapping of the BNNT film surface using an SEM-EDX image measured at an observation magnification of 1000 to 4000 times.
- measurement can be performed with an acceleration voltage of 10 kV, an emission current of 1 ⁇ A, a measurement pixel count of 256 ⁇ 256 pixels, and an integration count of 50 times.
- the surface can be treated with gold, platinum, osmium, or the like by a method such as vacuum deposition or sputtering.
- the pellicle film of the present invention preferably has a transmittance of 80% or more, more preferably 90% or more, for EUV (13.5 nm wavelength) light. This transmittance can be measured using a normal transmittance measuring machine.
- a normal pellicle is composed of a pellicle frame, a pellicle film, a pellicle film adhesive layer, a photomask substrate or exposure original plate adhesive layer (hereinafter referred to as mask adhesive layer), air vents, a filter, and the like. Also, a separator can usually be attached to protect the surface of the mask adhesive layer.
- the dimension (size) of the pellicle membrane is appropriately selected according to the size of the pellicle frame used.
- the thickness of the pellicle film is typically 10-200 nm.
- Adhesive can be used when attaching the pellicle frame to the pellicle membrane.
- Specific examples include fluoropolymers such as acrylic resin adhesives, epoxy resin adhesives, silicone resin adhesives, and fluorine-containing silicone adhesives.
- a silicone adhesive is preferable from the viewpoint of heat resistance.
- the adhesive is diluted with a solvent as necessary and applied to the top surface of the pellicle frame.
- a method using a brush, a spray, an automatic dispenser, or the like is adopted.
- the mask adhesive layer for attaching the pellicle to the mask substrate can be formed with a known adhesive such as double-sided adhesive tape, silicone adhesive, or acrylic adhesive.
- a mask adhesive layer is formed on the lower end surface of the pellicle frame, and a separator is attached releasably.
- the material of the pellicle frame is not particularly limited, and known materials can be used. Since EUV exposure requires higher accuracy than Arf exposure, the demand for flatness of the photomask is strict. It is known that the flatness of the photomask is affected by the pellicle. In order to minimize the influence of the pellicle on the photomask, it is preferable to use lightweight titanium, titanium alloy, aluminum, or aluminum alloy.
- the dimensions of the pellicle frame are not particularly limited, but if the height of the pellicle for EUV is limited to 2.5 mm or less, the thickness of the pellicle frame for EUV is smaller than that, and may be 2.5 mm or less. preferable.
- the thickness of the pellicle frame for EUV is preferably 1.5 mm or less in consideration of the thickness of the pellicle film, the photomask adhesive, and the like.
- the lower limit of the thickness of the pellicle frame is preferably 1.0 mm or more.
- the pellicle frame may be provided with vents or notches to accommodate changes in atmospheric pressure inside and outside the pellicle.
- a filter may then be provided to prevent foreign matter from passing through the vent.
- a release layer (separator) for protecting the adhesive may be attached to the lower end surface of the mask-side adhesive of the pellicle frame.
- the material of the release layer is not particularly limited, but for example polyethylene terephthalate (PET), polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), polyethylene (PE), polycarbonate (PC ), polyvinyl chloride (PVC), polypropylene (PP), etc. can be used.
- a release agent such as a silicone-based release agent or a fluorine-based release agent may be applied to the surface of the release layer.
- the pellicle frame of the present invention may be provided with protrusions facing outward or inward.
- a filter can also be formed by using such projections.
- a connection mechanism screw, adhesive, etc.
- the pellicle of the present invention is used not only as a protective member for suppressing the adhesion of foreign matter to the exposure original plate in the EUV exposure apparatus, but also to protect the exposure original plate during storage and transportation of the exposure original plate. It is good also as a protection member.
- Methods for manufacturing a pellicle-equipped exposure master plate by attaching a pellicle to an exposure master plate such as a photomask include the above-described method of attaching the pellicle with the photomask adhesive, an electrostatic adsorption method, a mechanical fixing method, and the like. be.
- a method for manufacturing a semiconductor or a liquid crystal display panel includes a step of exposing a substrate (semiconductor wafer or liquid crystal master plate) with the above exposure master plate with a pellicle.
- a substrate semiconductor wafer or liquid crystal master plate
- the exposure original plate with the pellicle is placed on a stepper and exposed. do.
- EUV exposure uses a projection optical system in which EUV light is reflected by an exposure master and guided to a substrate, and these are performed under reduced pressure or vacuum.
- the yield in the lithography process can be improved by using the exposure original plate with a pellicle.
- Example 1 Using amine borane borazine (B 3 N 3 H 6 ) as a raw material, it was reacted with nickelocene in ammonia at 1200 to 1300° C. to synthesize BNNT.
- the synthesized BNNTs were deposited on a hydrophobic filter (trade name “Advantech Membrane/T020A-293D” manufactured by Sansho Co., Ltd.) to form a multilayer BNNT film.
- a Si frame obtained by processing a Si wafer as a support the BNNT deposited on the filter is peeled off.
- An acrylic adhesive [manufactured by Soken Chemical Co., Ltd.
- SK-1499M is applied to one end surface of the support (the part that contacts the BNNT), and after curing, it is pressed against the BNNT film at a peeling speed of 0.1 mm. / s.Then, the BNNT film is transferred from the support to a pellicle frame, which has outer dimensions of 118.3 mm ⁇ 150.8 mm ⁇ 1.5 mm and inner dimensions of 142.8 mm ⁇ 142.8 mm. A 110.3 mm ⁇ 1.5 mm titanium pellicle frame was used, and a silicone-based adhesive (“KE-101A/B” manufactured by Shin-Etsu Chemical Co., Ltd.) applied to the upper end surface of the pellicle frame was cured by heating.
- KE-101A/B manufactured by Shin-Etsu Chemical Co., Ltd.
- the upper end face side of the pellicle frame was attached to the BNNT film attached to the support larger than the pellicle frame, and the portion outside the pellicle frame was removed to complete the pellicle.
- EUV transmittance measurement The EUV transmittance was measured as follows.
- the pellicle was irradiated with light (EUV) having a wavelength of 13.5 nm using an EUV irradiation apparatus (New Subaru (facility name) BL-10, University of Hyogo).
- the direction of EUV irradiation was set perpendicular to the pellicle film surface, and the EUV transmittance was measured by irradiating the pellicle film so as to scan it. As a result, the EUV transmittance was 95%.
- EUV durability> The pellicle was irradiated with EUV at a wavelength of 13.5 nm and a light source intensity of 5 W/cm 2 for 3 hours using an EUV irradiation apparatus (New Subaru (facility name) BL-9, University of Hyogo). The EUV durability was evaluated by observing the appearance before and after the durability test. As a result, no change in the appearance of the pellicle was observed before and after the durability test.
Abstract
Description
1.窒化ホウ素ナノチューブを有する膜(BNNT膜)を含むことを特徴とするペリクル膜。
2.BNNT膜は、BNNTの束を有するメッシュ、ウェブ又はグリッドを含む上記1記載のペリクル膜。
3.ペリクル膜の厚み全体に占めるBNNT膜の厚みの割合は90%以上である上記1又は2記載のペリクル膜。
4.13.5nmの波長を有する光に対して、透過率が80%以上である上記1~3のいずれかに記載のペリクル膜。
5.13.5nm波長を主露光波長として使用する極紫外線(EUV)光の露光に用いられる上記1~4のいずれかに記載のペリクル膜。
6.ペリクル膜とペリクルフレームとから構成され、該ペリクル膜が接着剤を介して上記ペリクルフレームの一端面に設けられるフォトリソグラフィ用ペリクルであって、上記ペリクル膜が上記1~5のいずれかに記載のペリクル膜であることを特徴とするペリクル。
7.露光原版に上記6記載のペリクルが装着されていることを特徴とするペリクル付き露光原版。
8.露光原版が、EUV用露光原版である上記7記載のペリクル付き露光原版。
9.上記8記載のペリクル付き露光原版を用いて露光することを特徴とする露光方法。
10.上記7記載のペリクル付き露光原版を用いて、真空下又は減圧下において基板を露光する工程を備えることを特徴とする半導体の製造方法。
11.上記7記載のペリクル付き露光原版を用いて、真空下又は減圧下において基板を露光する工程を備えることを特徴とする液晶表示板の製造方法。
12.上記7記載のペリクル付き露光原版を用いて、基板をEUV露光する工程を備えることを特徴とする半導体の製造方法。
13.上記7記載のペリクル付き露光原版を用いて、基板をEUV露光する工程を備えることを特徴とする液晶表示板の製造方法。
本発明のペリクル膜は、窒化ホウ素ナノチューブからなる膜(BNNT膜)である。以下、窒化ホウ素ナノチューブを有する膜を「BNNT膜」と略して記載する。本発明において、BNNT膜は、90質量%以上の窒化ホウ素ナノチューブを有することが好ましく、95質量%以上の窒化ホウ素ナノチューブを有することがより好ましく、98質量%以上の窒化ホウ素ナノチューブを有することが特に好ましく、実質的に窒化ホウ素ナノチューブからなることが本発明の効果を最大限に得ることができるため極めて好ましい。ここで、「実質的に窒化ホウ素ナノチューブからなる」とは、触媒や不純物成分を除いた膜の成分が窒化ホウ素ナノチューブからなることを意味する。また、本発明の効果を利用できる範囲において、カーボンナノチューブなどの各種材料との複合化をしてもよい。
<BNNT膜の製造方法>
BNNTは、浮遊触媒CVD法を利用して合成することができる。アミンボランボラジン(B3N3H6)またはデカボランB10H14を原料とし、アンモニア中でニッケロセンと1200~1300℃で反応させることで、BNNTを合成することができる。合成されたBNNTは、疎水性フィルタ上に堆積されるが、BNNT同士に作用する分子間力(ファンデルワールス力)により、互いに凝集して膜を形成することができる。ペリクルフレームとは異なる第二の支持体を用い、これによりフィルタ上に堆積されたBNNTを剥離し、該支持体からペリクルフレームへBNNT膜を転写する。ペリクルフレームの上端面に塗工したシリコーン系粘着剤(例えば、信越化学工業(株)製「KE-101A/B」)を加熱硬化後、上記支持体に張設されたBNNT膜(該支持体内部)に接触させる。ペリクルフレームより大きな該支持体に張り付けたBNNT膜にペリクルフレームの上端面側を貼り付け、ペリクルフレームよりも外側の部分を除去しペリクルを完成させることができる。
アミンボランボラジン(B3N3H6)を原料とし、アンモニア中でニッケロセンと1200~1300℃で反応させ、BNNTを合成した。合成したBNNTを疎水性フィルタ(商品名「アドバンテック メンブラン/T020A-293D」(株)三商製)上に堆積し、多層のBNNT膜を形成した。次に、支持体として、Siウエハを加工して得られたSi枠体を用い、フィルタ上に堆積されたBNNTを剥離する。上記支持体の片側端面(BNNTに接触する部分)にアクリル系粘着剤〔綜研化学(株)製「SK-1499M)〕を塗工し、硬化後、BNNT膜に押し当てて剥離速度0.1mm/sで傾斜剥離を行う。その後、該支持体からペリクルフレームへBNNT膜を転写する。ペリクルフレームとしては、外寸:118.3mm×150.8mm×1.5mm、内寸:142.8mm×110.3mm×1.5mmのチタン製ペリクルフレームを用いた。このペリクルフレームの上端面に塗工したシリコーン系粘着剤(信越化学工業(株)製「KE-101A/B」)を加熱硬化後、上記支持体に張設されたBNNT膜(該支持体内部)に接触させる。ペリクルフレームより大きな該支持体に張り付けたBNNT膜にペリクルフレームの上端面側を貼り付け、ペリクルフレームよりも外側の部分を除去しペリクルを完成させた。
EUV透過率は、以下のように行った。
EUV照射装置(ニュースバル(施設名)BL-10、兵庫県立大学)にて、波長13.5nmの光(EUV)をペリクルに照射した。EUVの照射方向はペリクル膜面に対して垂直方向とし、ペリクル膜上を走査するように照射し、EUV透過率を測定した。その結果、EUV透過率は95%であった。
EUV照射装置(ニュースバル(施設名)BL-9、兵庫県立大学)にて、波長13.5nm、光源強度5W/cm2のEUVを3時間の条件でペリクルに照射した。EUV耐久性については、耐久試験前後の外観観察によって評価した。その結果、耐久試験の前後でペリクルの外観変化は見られなかった。
Claims (13)
- 窒化ホウ素ナノチューブを有する膜(BNNT膜)を含むことを特徴とするペリクル膜。
- BNNT膜は、BNNTの束を有するメッシュ、ウェブ又はグリッドを含む請求項1記載のペリクル膜。
- ペリクル膜の厚み全体に占めるBNNT膜の厚みの割合は90%以上である請求項1又は2記載のペリクル膜。
- 13.5nmの波長を有する光に対して、透過率が80%以上である請求項1~3のいずれか1項記載のペリクル膜。
- 13.5nm波長を主露光波長として使用する極紫外線(EUV)光の露光に用いられる請求項1~4のいずれか1項記載のペリクル膜。
- ペリクル膜とペリクルフレームとから構成され、該ペリクル膜が接着剤を介して上記ペリクルフレームの一端面に設けられるフォトリソグラフィ用ペリクルであって、上記ペリクル膜が請求項1~5のいずれか1項記載のペリクル膜であることを特徴とするペリクル。
- 露光原版に請求項6記載のペリクルが装着されていることを特徴とするペリクル付き露光原版。
- 露光原版が、EUV用露光原版である請求項7記載のペリクル付き露光原版。
- 請求項8記載のペリクル付き露光原版を用いて露光することを特徴とする露光方法。
- 請求項7記載のペリクル付き露光原版を用いて、真空下又は減圧下において基板を露光する工程を備えることを特徴とする半導体の製造方法。
- 請求項7記載のペリクル付き露光原版を用いて、真空下又は減圧下において基板を露光する工程を備えることを特徴とする液晶表示板の製造方法。
- 請求項7記載のペリクル付き露光原版を用いて、基板をEUV露光する工程を備えることを特徴とする半導体の製造方法。
- 請求項7記載のペリクル付き露光原版を用いて、基板をEUV露光する工程を備えることを特徴とする液晶表示板の製造方法。
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