TW201334031A - 光固化產物及製造彼之方法 - Google Patents
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- RMBPEFMHABBEKP-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2C3=C[CH]C=CC3=CC2=C1 RMBPEFMHABBEKP-UHFFFAOYSA-N 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
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- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- IIRDTKBZINWQAW-UHFFFAOYSA-N hexaethylene glycol Chemical compound OCCOCCOCCOCCOCCOCCO IIRDTKBZINWQAW-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
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- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 235000013847 iso-butane Nutrition 0.000 description 1
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- QDLAGTHXVHQKRE-UHFFFAOYSA-N lichenxanthone Natural products COC1=CC(O)=C2C(=O)C3=C(C)C=C(OC)C=C3OC2=C1 QDLAGTHXVHQKRE-UHFFFAOYSA-N 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 229910001338 liquidmetal Inorganic materials 0.000 description 1
- FSPSELPMWGWDRY-UHFFFAOYSA-N m-Methylacetophenone Chemical compound CC(=O)C1=CC=CC(C)=C1 FSPSELPMWGWDRY-UHFFFAOYSA-N 0.000 description 1
- VSQYNPJPULBZKU-UHFFFAOYSA-N mercury xenon Chemical compound [Xe].[Hg] VSQYNPJPULBZKU-UHFFFAOYSA-N 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- OLXYLDUSSBULGU-UHFFFAOYSA-N methyl pyridine-4-carboxylate Chemical compound COC(=O)C1=CC=NC=C1 OLXYLDUSSBULGU-UHFFFAOYSA-N 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012170 montan wax Substances 0.000 description 1
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
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- 229920001778 nylon Polymers 0.000 description 1
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- AUBNVERMHFAAKM-UHFFFAOYSA-M octane-1-sulfonate;triphenylsulfanium Chemical compound CCCCCCCCS([O-])(=O)=O.C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 AUBNVERMHFAAKM-UHFFFAOYSA-M 0.000 description 1
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- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003566 oxetanyl group Chemical group 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
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- YNXCGLKMOXLBOD-UHFFFAOYSA-N oxolan-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CCCO1 YNXCGLKMOXLBOD-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- QBDSZLJBMIMQRS-UHFFFAOYSA-N p-Cumylphenol Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=CC=C1 QBDSZLJBMIMQRS-UHFFFAOYSA-N 0.000 description 1
- 229930184652 p-Terphenyl Natural products 0.000 description 1
- NKTOLZVEWDHZMU-UHFFFAOYSA-N p-cumyl phenol Natural products CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-UHFFFAOYSA-N 0.000 description 1
- LXTZRIBXKVRLOA-UHFFFAOYSA-N padimate a Chemical compound CCCCCOC(=O)C1=CC=C(N(C)C)C=C1 LXTZRIBXKVRLOA-UHFFFAOYSA-N 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 229960004692 perflenapent Drugs 0.000 description 1
- 125000005003 perfluorobutyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 1
- 125000005004 perfluoroethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 125000005005 perfluorohexyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 1
- 125000005007 perfluorooctyl group Chemical group FC(C(C(C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)* 0.000 description 1
- NJCBUSHGCBERSK-UHFFFAOYSA-N perfluoropentane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F NJCBUSHGCBERSK-UHFFFAOYSA-N 0.000 description 1
- 125000005009 perfluoropropyl group Chemical group FC(C(C(F)(F)F)(F)F)(F)* 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
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- 125000004076 pyridyl group Chemical group 0.000 description 1
- WVIICGIFSIBFOG-UHFFFAOYSA-N pyrylium Chemical class C1=CC=[O+]C=C1 WVIICGIFSIBFOG-UHFFFAOYSA-N 0.000 description 1
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- 239000011342 resin composition Substances 0.000 description 1
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- 150000003335 secondary amines Chemical group 0.000 description 1
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- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
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- 238000004544 sputter deposition Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 238000003860 storage Methods 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
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- 238000004381 surface treatment Methods 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
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- OKYDCMQQLGECPI-UHFFFAOYSA-N thiopyrylium Chemical class C1=CC=[S+]C=C1 OKYDCMQQLGECPI-UHFFFAOYSA-N 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- MAKDTFFYCIMFQP-UHFFFAOYSA-N titanium tungsten Chemical compound [Ti].[W] MAKDTFFYCIMFQP-UHFFFAOYSA-N 0.000 description 1
- RLGKSXCGHMXELQ-ZRDIBKRKSA-N trans-2-styrylquinoline Chemical compound C=1C=C2C=CC=CC2=NC=1\C=C\C1=CC=CC=C1 RLGKSXCGHMXELQ-ZRDIBKRKSA-N 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- UZPUXLRDLVOKTB-UHFFFAOYSA-N trifluoromethyl benzenesulfonate Chemical compound FC(F)(F)OS(=O)(=O)C1=CC=CC=C1 UZPUXLRDLVOKTB-UHFFFAOYSA-N 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C33/00—Moulds or cores; Details thereof or accessories therefor
- B29C33/56—Coatings, e.g. enameled or galvanised; Releasing, lubricating or separating agents
- B29C33/60—Releasing, lubricating or separating agents
- B29C33/62—Releasing, lubricating or separating agents based on polymers or oligomers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
- H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
- H01L21/0274—Photolithographic processes
-
- 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
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
- B29C39/02—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor for making articles of definite length, i.e. discrete articles
- B29C39/026—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor for making articles of definite length, i.e. discrete articles characterised by the shape of the surface
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y15/00—Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
- G03F1/68—Preparation processes not covered by groups G03F1/20 - G03F1/50
- G03F1/76—Patterning of masks by imaging
-
- 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
- G03F7/0002—Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping
-
- 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
- G03F7/004—Photosensitive materials
- G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
-
- 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
- G03F7/004—Photosensitive materials
- G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
-
- 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
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
-
- 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
- G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
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Abstract
本發明意圖提供光固化產物,其係使用光壓印法製得並具有有利的圖案準確度及改良圖案缺陷。本發明提出藉由以光照射與模具接觸的塗膜而得的光固化產物,該光固化產物含有含氟原子的界面活性劑,其中以飛行時間二次離子質譜術為基礎,藉光固化產物之表面分析而得的二次離子訊號中,C2H5O+離子訊號的強度高於C3H7O+離子訊號的強度。
Description
本發明係關於光固化產物及製造彼之方法。
近年來,半導體積體電路越來越精細且更整體化。光蝕刻法常作為用於半導體之形成圖案的技術。但是,以光蝕刻法為基礎之越來越精細的圖案無法超越曝光的繞射極限。
因此,提出奈米壓印法以進一步促進較精細且較高準確電路。該奈米壓印法是指薄膜形成圖案的技術,其含括將具有精細上凸/下凹圖案的模具壓在經薄樹脂膜塗覆的基板上以將模具中之上凸/下凹圖案轉印至經薄樹脂膜塗覆的基板。
奈米壓印法中,光奈米壓印法揭示於,例如,受到注入的NPL 1。該光奈米壓印法含括:將透光的模具壓印在經光可固化組成物塗覆的基板上;藉由照光令光可固化組成物固化;及所得的光固化產物自模具脫模以製造精細之阻抗圖案積體化的基板。
但是,使用光奈米壓印法必須解決一些問
題。問題之一在於模具自固化產物脫模所須的力(即,脫模力)大。因為此脫模力大,所以光壓印法具有缺點,如圖案缺陷及在模具和基板之間的對準之精準度降低的問題,其因基板自台座脫離所致。
因應此等問題,PTL 1揭示一種用於壓印的光固化產物,包括置於基板側上的深部零件和置於深部零件上的表面零件,該表面零件的氟化合物含量高於深部零件。或者,PTL 2揭示用於光壓印的光可固化組成物,其包括至少一種光可聚合單體、光聚合引發劑、和含氟原子的界面活性劑。
PTL 1中揭示的光固化產物試圖藉由表面零件中所含的氟化合物降低表面能量,藉此降低模具自光固化產物脫模期間內產生的脫模力。PTL 2亦試圖在類似於PTL 1的原理下,使用含有含氟原子的界面活性劑之光可固化組成物來降低脫模力。可惜地,PTL 1和PTL 2中揭示的光可固化樹脂組成物之降低脫模力的效果不足。
參考文獻
專利案
PTL 1:日本專利申請案公開第2006-080447號
PTL 2:日本專利申請案公開第2007-084625號
非專利案
NPL 1 : Proc. SPIE 3676, Emerging Lithographic Technologies III, P. 379, 1999
本發明用以解決慣用技術問題,本發明之目的係提出使用光壓印法製得並具有有利的圖案精確度和改良的圖案缺陷的光固化產物。
本發明之光固化產物係一種藉由以光照射與模具接觸的光可固化組成物而得之光固化產物,該光固化產物含有含氟原子的界面活性劑,其中以飛行時間二次離子質譜術為基礎,藉光固化產物之表面分析而得的二次離子訊號中,C2H5O+離子訊號的強度高於C3H7O+離子訊號的強度。
本發明之光固化產物自模具脫模僅須小脫模力。因此,本發明可提供使用光壓印法製得並具有有利的圖案精確性和改良的圖案缺陷之光固化產物。
由例示具體實施例的以下描述及附圖將明瞭本發明的其他特徵。
1‧‧‧圖案複製層
2‧‧‧基板
3‧‧‧模具
4‧‧‧照射光
10‧‧‧塗膜
11‧‧‧固化膜
圖1A、1B、1C、1D、1E和1F為截面圖,其出示本發明之光固化產物之製法的一個例子。
下文中將參考附圖適切地詳細描述本發明之具體實施例。然而,僅將下述具體實施例視為說明且無限
制性。以下描述的具體實施例中,可以基於嫻於此技術者的一般知識,以未背離本發明之精神的方式作出適當的改變、修飾等且其可含括於本發明之範圍內。
光固化產物
首先,將描述本發明之光固化產物。本發明之光固化產物係藉由以光照射與模具接觸的塗膜而得。本發明中,用以製造本發明之光固化產物之塗膜可為藉由以下述光可固化組成物塗覆基板之類而形成的薄膜。
本發明之光固化產物具有以下特徵(a)和(b):(a)光固化產物含有含氟原子的界面活性劑;和(b)以飛行時間二次離子質譜術為基礎,藉(光固化產物之)表面分析而得的二次離子訊號中,C2H5O+離子訊號的強度高於C3H7O+離子訊號的強度。
本發明者發現在模具自光固化產物脫模期間內形成的脫模力可藉由滿足條件(a)和(b)而降低。
下文中,將詳細描述本發明之光固化產物。
(1)光固化產物
本發明之光固化產物係藉照光得到的聚合物化合物。特定言之,本發明之光固化產物係自含有經由光化學反應形成自由基或陽離子的化合物(光聚合引發劑)和可聚合的單體之光可固化組成物製得。下文將描述該光可固化組成物的細節。
(2)含氟原子的界面活性劑
本發明之光固化產物中所含之含氟原子的界面活性劑主要分佈在本發明的光固化產物表面並在本發明之光固化產物自模具脫模的期間內扮演降低脫模力的角色。
本發明中,含氟原子的界面活性劑可含於光固化產物中例如下列方式(i)至(iii):(i)含氟原子的界面活性劑含於光固化產物中作為光可固化組成物的一種組份;(ii)表面經含氟原子的界面活性劑塗覆的模具與不含含氟原子的界面活性劑之光可固化組成物接觸,使得含氟原子的界面活性劑在照光之前轉移至光可固化組成物;和(iii)表面經含氟原子的界面活性劑塗覆的模具與不含含氟原子的界面活性劑之光可固化組成物接觸並照光以使得含氟原子的界面活性劑轉移至光固化產物。
此處,在以方式(ii)或(iii)使用表面經含氟原子的界面活性劑塗覆的模具的情況中,重覆壓印會造成模具之經含氟原子的界面活性劑塗覆的表面逐漸脫離表面。反之,在以方式(i)使用光可固化組成物中所含之含氟原子的界面活性劑的情況中,含氟原子的界面活性劑恆定地施於模具和光固化產物,即使於重覆壓印期間內亦然。因此,以此方式達到極佳的重覆耐久性。方式(i)至(iii)中,以方式(i)為較佳。
(3)以TOF-SIMS為基礎,光固化產物之表面分析TOF-SIMS是一種檢測存在於固態樣品表面上之原子或分子類型的分析方法。下文中,將約略描述此方法的梗概。
在藉由以快速離子束脈衝(原始離子)在高真空中照射之後,藉由噴濺現象,固態樣品表面產生帶正或負電的離子(二次離子),並在真空中釋出這些二次離子。藉電場而使得這些二次離子集中在一個方向,並自與其有一段距離處偵測。根據樣品表面之組成,樣品表面產生質量不同的各種二次離子。較輕的離子飛行較快,而較重的離子飛行較慢。因此,可藉由測定產生二次離子至其被偵測到的時間(飛行時間)分析所產生的二次離子的質量。以原始離子照射之後,固態樣品在真空中僅釋出固態樣品之最外表面產生的二次離子。因此,可得到關於樣品表面(約數奈米深度)的資訊。
所得數據係質子光譜,其中以m/z(m:二次離子質量,z:電荷比)作為橫座標及偵測到的離子計數作為縱座標地作圖。此處,自此質譜橫座標上的訊號位置(下文中,亦稱為峰)定出二次離子的質量。自此質量定出二次離子的元素組成。同時,可自峰在質譜中的高度或面積評估二次離子的訊號強度。
TOF-SIMS中得到的大部分二次離子是伴隨原始離子照射,分子結構之分解作用(破碎作用)形成的破碎離子。形成的破碎離子中,具有氫(H)、碳(C)、和氧(O)的
離子可以作為各種有機化合物的起源。反映主要存在於樣品表面之有機化合物之次結構的破碎離子會構成具有高訊號強度的峰。因此,可測得並評估形成之破碎離子形式之二次離子的元素組成和訊號強度,藉此預測主要存在於光固化產物表面之分子的次結構或物種。
本發明中,重要的破碎離子是C2H5O+離子(m/z=45)和C3H7O+離子(m/z=59)。生成C2H5O+離子的可能來源主要是在次結構中含有環氧乙基(-CH2CH2O-)作為重覆單元之類的化合物。另一方面,生成C3H7O+離子的可能來源主要是在次結構中含有環氧丙基(-CH2CH2CH2O-)作為重覆單元之類的化合物。此處,本發明之光固化產物的特徵在於藉TOF-SIMS得到的碎片中,C2H5O+離子的數目高於C3H7O+離子。此意謂光固化產物的表面部分主要具有環氧乙基(-CH2CH2O-),而非環氧丙基(-CH2CH2CH2O-)。但是,此並非意謂光固化產物表面的次結構(其作為離子C2H5O+來源)被環氧乙基(-CH2CH2O-)所佔據。
此處,具有環氧乙基(-CH2CH2O-)的化合物,其為本發明之光固化產物中之生成C2H5O+離子的主要來源,可為光固化產物賴以為基礎的聚合物化合物,或含氟原子的界面活性劑。
特別是具有環氧乙基之含氟原子的界面活性劑可用於本發明的確實原因仍待闡釋。但是,由含有環氧乙基的次結構或其他次結構對於含氟原子的界面活性劑以外的化合物分子之親和力的觀點,可以作出一些假設。可
能的假設述於,例如,以下(i)至(iii):
(i)第一個假設
第一個可能的假設在於:由於環氧乙烷對於氟原子的親和力不及環氧丙烷,所以在環氧乙烷和附於模具側上之含氟原子的界面活性劑中的氟原子之間形成界面,使得其間的親和力進一步降低以降低脫模力。
(ii)第二個假設
第二個可能的假設在於:由於環氧乙烷對於可聚合單體的親和性不及環氧丙烷,所以結構上含有環氧乙烷之含氟原子的界面活性劑具有較高的表面隔離效果,並因此而增進了藉氟降低脫模力的效果。
(iii)第三個假設
第三個可能的假設在於:由於環氧乙烷對於石英的親和力高於環氧丙烷,所以結構上含有環氧乙烷之含氟原子的界面活性劑較易藉之後描述的光壓印法接合至模具表面,並因此而藉氟增進降低脫模力的效果。
(3)TOF-SIMS測定
之後,將描述TOF-SIMS測定法。
就離子化效能、質量解析度等的觀點,一般的液態金屬離子(如Ga+)和簇離子(如Au3 +或Bi3 +)可作為
TOF-SIMS方法中的原始離子物種。但是,本發明中,TOF-SIMS測定中使用的原始離子不限於這些離子。
適用於TOF-SIMS測定的分析條件無法簡單或明確地界定。下文將描述典型條件。特定言之,原始離子脈衝頻率範圍由1 kHz至50 kHz;原始離子束能量範圍由12 keV至25 keV;而原始離子束脈衝寬度範圍由0.5毫微秒至10毫微秒。在絕緣體樣品的情況中,樣品表面可經電子束中和。原始離子束在10微米至500微米見方的測量面積中之16至512次重覆掃描可以64至512像素見方的像素面積進行,藉此同時得到測量面積的質譜和二次離子的二次分佈影像。
藉TOF-SIMS測定得到的各離子的訊號強度可以自所得質譜之位於所欲m/z之選定峰的高度或面積計算。
本發明中,至少計算C2H5O+離子(m/z=45)和C3H7O+離子(m/z=59)的個別訊號強度。
本發明中,可計算C2H5O+離子和C3H7O+離子以外的二次離子的訊號強度。例如,亦可計算F+離子(m/z=19)的訊號強度以證實含氟原子的界面活性劑的氟基存在於表面。同樣地,在使用(甲基)丙烯酸化合物作為可聚合單體的情況中,可計算C3H3O+離子(m/z=55)的訊號強度以證實丙烯醯基存在於光聚合反應產物表面。
考慮樣品表面的平面內分佈,可於多個區域進行前述的TOF-SIMS測量,並可得到所得值之平均。或
者,可以分段光柵測量模式評估樣品的全表面以計算其訊號強度。
光可固化組成物
下文中,將描述本發明的光可固化組成物。本發明的光可固化組成物具有至少一種可聚合的單體、光聚合引發劑、和含氟原子的界面活性劑。下文中,將描述光可固化組成物中所含的各組份。
(1)可聚合單體(組份A)
本發明之光可固化組成物中所含的可聚合單體(組份A)包括自由基可聚合的單體和陽離子可聚合的單體。
(1-1)自由基可聚合的單體
特定言之,具有一或多個丙烯醯基(CH2=CHCOO-)或甲基丙烯醯基(CH2=C(CH3)COO-)之化合物可作為自由基可聚合的單體。
具有一個丙烯醯基或甲基丙烯醯基之單官能性(甲基)丙烯酸系化合物的例子包括,但不限於,苯氧基(甲基)丙烯酸乙酯、(甲基)丙烯酸苯氧基-2-甲基乙酯、(甲基)丙烯酸苯氧基乙氧基乙酯、(甲基)丙烯酸3-苯氧基-2-羥基丙酯、(甲基)丙烯酸2-苯基苯氧基乙酯、(甲基)丙烯酸4-苯基苯氧基乙酯、(甲基)丙烯酸3-(2-苯基苯基)-2-羥基丙酯、對-枯基酚與環氧乙烷反應之(甲基)丙烯酸酯、
(甲基)丙烯酸2-溴苯氧基乙酯、(甲基)丙烯酸2,4-二溴苯氧基乙酯、(甲基)丙烯酸2,4,6-三溴苯氧基乙酯、經二或更多莫耳環氧乙烷或環氧丙烷改質的(甲基)丙烯酸苯氧酯、聚氧伸乙基壬基苯基醚(甲基)丙烯酸酯、(甲基)丙烯酸異酯、(甲基)丙烯酸1-金剛酯、(甲基)丙烯酸2-甲基-2-金剛酯、(甲基)丙烯酸2-乙基-2-金剛酯、(甲基)丙烯酸酯、(甲基)丙烯酸三環癸酯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸二環戊烯酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸4-丁基環己酯、丙烯醯基嗎啉、(甲基)丙烯酸2-羥乙酯、(甲基)丙烯酸2-羥丙酯、(甲基)丙烯酸2-羥丁酯、(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸三級丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸異戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸十一烷酯、(甲基)丙烯酸十二烷酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸異硬脂酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸四氫糠酯、(甲基)丙烯酸丁氧基乙酯、(甲基)丙烯酸乙氧基二乙二醇酯、單(甲基)丙烯酸聚乙二醇酯、單(甲基)丙烯酸聚丙二醇酯、(甲基)丙烯酸甲氧基乙二醇酯、(甲基)丙烯酸乙氧基乙酯、(甲基)丙烯酸甲氧基聚乙二醇酯、(甲基)丙烯酸甲氧
基聚丙二醇酯、二丙酮(甲基)丙烯醯胺、異丁氧基甲基(甲基)丙烯醯胺、N,N-二甲基(甲基)丙烯醯胺、三級辛基(甲基)丙烯醯胺、(甲基)丙烯酸二甲胺基乙酯、(甲基)丙烯酸二乙胺基乙酯、(甲基)丙烯酸7-胺基-3,7-二甲基辛酯、N,N-二乙基(甲基)丙烯醯胺、和N,N-二甲胺基丙基(甲基)丙烯醯胺。
前述化合物中,市售單官能性(甲基)丙烯酸系化合物的例子包括,但不限於,Aronix M101,M102,M110,M111,M113,M117,M5700,TO-1317,M120,M150,和M156(皆由Toagosei Co.,Ltd.製造),MEDOL10,MIBDOL10,CHDOL10,MMDOL30,MEDOL30,MIBDOL30,CHDOL30,LA,IBXA,2-MTA,HPA,和Biscoat #150,#155,#158,#190,#192,#193,#220,#2000,#2100,和#2150(皆由Osaka Organic Chemical Industry,Ltd.製造),Light Acrylate BO-A,EC-A,DMP-A,THF-A,HOP-A,HOA-MPE,HOA-MPL,PO-A,P-200A,NP-4EA,和NP-8EA,和epoxy ester M-600A(皆由Kyoeisha Chemical Co.,Ltd.製造),KAYARAD TC110S,R-564,和R-128H(皆由Nippon Kayaku Co.,Ltd.製造),NK ester AMP-10G和AMP-20G(皆由Shin-Nakamura Chemical Co.,Ltd.製造),FA-511A,512A,和513A(皆由Hitachi Chemical Co.,Ltd.製造),PHE,CEA,PHE-2,PHE-4,BR-31,BR-31M,和BR-32(皆由Dai-Ichi Kogyo Seiyaku Co.,Ltd.製造),VP(由BASF製造),和ACMO,DMAA和DMAPAA
(皆由Kohjin Holdings Co.,Ltd.製造)。
具有二或更多個丙烯醯基或甲基丙烯醯基的多官能性(甲基)丙烯酸系化合物的例子包括,但不限於,三羥甲基丙烷二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、經EO-改質的三羥甲基丙烷三(甲基)丙烯酸酯、經PO-改質的三羥甲基丙烷三(甲基)丙烯酸酯、經EO,PO-改質的三羥甲基丙烷三(甲基)丙烯酸酯、三(甲基)丙烯酸季戊四醇酯、四(甲基)丙烯酸季戊四醇酯、二(甲基)丙烯酸乙二醇酯、二(甲基)丙烯酸四乙二醇酯、二(甲基)丙烯酸聚乙二醇酯、二(甲基)丙烯酸聚丙二醇酯、二(甲基)丙烯酸1,4-丁二醇酯、二(甲基)丙烯酸1,6-己二醇酯、二(甲基)丙烯酸新戊二醇酯、三(甲基)丙烯酸參(2-羥乙基)異氰尿酸酯、參(丙烯醯氧基)異氰尿酸酯、雙(羥甲基)三環癸烷二(甲基)丙烯酸酯、五(甲基)丙烯酸二季戊四醇酯、六(甲基)丙烯酸二季戊四醇酯、經EO-改質的2,2-雙(4-((甲基)丙烯醯氧基)苯基)丙烷、經PO-改質的2,2-雙(4-((甲基)丙烯醯氧基)苯基)丙烷、和經EO,PO-改質的2,2-雙(4-((甲基)丙烯醯氧基)苯基)丙烷。
所述化合物中,市售多官能性(甲基)丙烯醯基化合物的例子包括,但不限於,Yupimer UV SA1002和SA2007(皆由Mitsubishi Chemical Corp.製造),Biscoat #195,#230,#215,#260,#335HP,#295,#300,#360,#700,GPT,和3PA(皆由Osaka Organic Chemical Industry,Ltd.製造),Light Acrylate 4EG-A,9EG-A,NP-
A,DCP-A,BP-4EA,BP-4PA,TMP-A,PE-3A,PE-4A,和DPE-6A(皆由Kyoeisha Chemical Co.,Ltd.製造),KAYARAD PET-30,TMPTA,R-604,DPHA,DPCA-20,-30,-60,和-120,HX-620,D-310,和D-330(皆由Nippon Kayaku Co.,Ltd.製造),Aronix M208,M210,M215,M220,M240,M305,M309,M310,M315,M325,和M400(皆由Toagosei Co.,Ltd.製造),和Ripoxy VR-77,VR-60,和VR-90(皆由Showa Highpolymer Co.,Ltd.製造)。
上述自由基可聚合的單體可以單獨使用或二或更多種類型併用。
上述化合物中,“(甲基)丙烯酸酯”是指分享共同酯部分的丙烯酸酯或甲基丙烯酸酯之組合。“(甲基)丙烯醯基”是指丙烯醯基和甲基丙烯醯基之組合。EO代表環氧乙烷。經EO-改質的化合物是指具有環氧乙烷基的嵌段結構。PO代表環氧丙烷。經PO-改質的化合物是指具有環氧丙烷基的嵌段結構。
(1-2)陽離子可聚合的單體
具有一或多個乙烯醚基(CH2=CH-O-)、環氧基、或氧呾基(oxetanyl)的化合物可作為陽離子可聚合的單體。
具有一個乙烯醚基之化合物的例子包括,但不限於,甲基乙烯醚、乙基乙烯醚、丙基乙烯醚、正丁基乙烯醚、三級丁基乙烯醚、2-乙基己基乙烯醚、正壬基乙
烯醚、月桂基乙烯醚、環己基乙烯醚、環己基甲基乙烯醚、4-甲基環己基甲基乙烯醚、苄基乙烯醚、二環戊烯基乙烯醚、2-二環戊烯氧基乙烯醚、甲氧基乙基乙烯醚、乙氧基乙基乙烯醚、丁氧基乙基乙烯醚、甲氧基乙氧基乙基乙烯醚、乙氧基乙氧基乙基乙烯醚、甲氧基聚乙二醇乙烯醚、四氫糠基乙烯醚、2-羥乙基乙烯醚、2-羥丙基乙烯醚、4-羥丁基乙烯醚、4-羥甲基環己基甲基乙烯醚、二乙二醇單乙烯醚、聚丙二醇乙烯醚、氯乙基乙烯醚、氯丁基乙烯醚、氯乙氧基乙基乙烯醚、苯基乙基乙烯醚、和苯氧基聚乙二醇乙烯醚。
具有二或更多個乙烯醚基的化合物的例子包括,但不限於,二乙烯醚,如乙二醇二乙烯醚、二乙二醇二乙烯醚、聚乙二醇二乙烯醚、丙二醇二乙烯醚、丁二醇二乙烯醚、己二醇二乙烯醚、雙酚A環氧烷二乙烯醚、和雙酚F環氧烷二乙烯醚;和多官能性乙烯醚,如三羥甲基乙烷三乙烯醚、三羥甲基丙烷三乙烯醚、二三羥甲基丙烷四乙烯醚、甘油三乙烯醚、季戊四醇四乙烯醚、二季戊四醇五乙烯醚、二季戊四醇六乙烯醚、三羥甲基丙烷三乙烯醚的環氧乙烷加合物、三羥甲基丙烷三乙烯醚的環氧丙烷加合物、二三羥甲基丙烷四乙烯醚的環氧乙烷加合物、二三羥甲基丙烷四乙烯醚的環氧丙烷加合物、季戊四醇四乙烯醚的環氧乙烷加合物、季戊四醇四乙烯醚的環氧丙烷加合物、二季戊四醇六乙烯醚的環氧乙烷加合物、和二季戊四醇六乙烯醚的環氧丙烷加合物。
具有一個環氧基的化合物的例子包括,但不限於,苯基環氧丙醚、對-三級丁基苯基環氧丙醚、丁基環氧丙醚、2-乙基己基環氧丙醚、烯丙基環氧丙醚、1,2-環氧丁烷、1,3-丁二烯一氧化物、1,2-環氧癸烷、表氯醇、1,2-環氧基癸烷、苯乙烯化氧、環氧己烷、3-甲基丙烯醯氧基甲基環氧己烷、3-丙烯醯氧基甲基環氧己烷、和3-乙烯基環氧己烷。
具有二或多個環氧基的化合物的例子包括,但不限於,雙酚A二環氧丙醚、雙酚F二環氧丙醚、雙酚S二環氧丙醚、溴化的雙酚A二環氧丙醚、溴化的雙酚F二環氧丙醚、溴化的雙酚S二環氧丙醚、環氧清漆樹脂、氫化的雙酚A二環氧丙醚、氫化的雙酚F二環氧丙醚、氫化的雙酚S二環氧丙醚、3,4-環氧基環己基甲基-3’,4’-環氧基環己烷羧酸酯、2-(3,4-環氧基環己基-5,5-螺-3,4-環氧基)環己烷-間-二噁烷、雙(3,4-環氧基環己基甲基)己二酸酯、乙烯基環氧己烷、4-乙烯基環氧基環己烷、雙(3,4-環氧基-6-甲基環己基甲基)己二酸酯、3,4-環氧基-6-甲基環己基-3’,4’-環氧基-6’-甲基環己烷羧酸酯、伸甲基雙(3,4-環氧基環己烷)、二環戊二烯基二環氧化物、乙二醇的二(3,4-環氧基環己基甲基)醚、伸乙基雙(3,4-環氧基環己烷羧酸酯)、環氧基六氫酞酸二辛酯、環氧基六氫酞酸二-2-乙基己酯、1,4-丁二醇二環氧丙醚、1,6-己二醇二環氧丙醚、甘油三環氧丙醚、三羥甲基丙烷三環氧丙醚、聚乙二醇二環氧丙醚、聚丙二醇二環氧丙
醚、1,1,3-十四碳二烯二氧化物、檸檬烯二氧化物、1,2,7,8-二環氧基辛烷、和1,2,5,6-二環氧基環辛烷。
具有一個氧呾基的化合物的例子包括,但不限於,3-乙基-3-羥甲基環氧丁烷、3-(甲基)烯丙氧基甲基-3-乙基環氧丁烷、(3-乙基-3-氧呾基甲氧基)甲基苯、4-氟-[1-(3-乙基-3-氧呾基甲氧基)甲基]苯、4-甲氧基-[1-(3-乙基-3-氧呾基甲氧基)甲基]苯、[1-(3-乙基-3-氧呾基甲氧基)乙基]苯基醚、異丁氧基甲基(3-乙基-3-氧呾基甲基)醚、異基氧基乙基(3-乙基-3-氧呾基甲基)醚、異基(3-乙基-3-氧呾基甲基)醚、2-乙基己基(3-乙基-3-氧呾基甲基)醚、乙基二乙二醇(3-乙基-3-氧呾基甲基)醚、二環戊二烯(3-乙基-3-氧呾基甲基)醚、二環戊烯氧基乙基(3-乙基-3-氧呾基甲基)醚、二環戊烯基(3-乙基-3-氧呾基甲基)醚、四氫糠基(3-乙基-3-氧呾基甲基)醚、四溴苯基(3-乙基-3-氧呾基甲基)醚、2-四溴苯氧基乙基(3-乙基-3-氧呾基甲基)醚、三溴苯基(3-乙基-3-氧呾基甲基)醚、2-三溴苯氧基乙基(3-乙基-3-氧呾基甲基)醚、2-羥乙基(3-乙基-3-氧呾基甲基)醚、2-羥丙基(3-乙基-3-氧呾基甲基)醚、丁氧基乙基(3-乙基-3-氧呾基甲基)醚、五氯苯基(3-乙基-3-氧呾基甲基)醚、五溴苯基(3-乙基-3-氧呾基甲基)醚、和基(3-乙基-3-氧呾基甲基)醚。
具有二或更多個氧呾基的化合物的例子包括,但不限於,多官能性環氧丁烷,如3,7-雙(3-氧呾基)-5-氧-壬烷、3,3’-(1,3-(2-甲基)丙二基雙(氧伸甲基))雙-(3-
乙基環氧丁烷)、1,4-雙[(3-乙基-3-氧呾基甲氧基)甲基]苯、1,2-雙[(3-乙基-3-氧呾基甲氧基)甲基]丙烷、1,3-雙[(3-乙基-3-氧呾基甲氧基)甲基]丙烷、乙二醇雙(3-乙基-3-氧呾基甲基)醚、二環戊烯基雙(3-乙基-3-氧呾基甲基)醚、三(乙二醇)雙(3-乙基-3-氧呾基甲基)醚、四(乙二醇)雙(3-乙基-3-氧呾基甲基)醚、三環癸二基二伸甲雙(3-乙基-3-氧呾基甲基)醚、三羥甲基丙烷參(3-乙基-3-氧呾基甲基)醚、1,4-雙(3-乙基-3-氧呾基甲氧基)丁烷、1,6-雙(3-乙基-3-氧呾基甲氧基)己烷、季戊四醇參(3-乙基-3-氧呾基甲基)醚、季戊四醇肆(3-乙基-3-氧呾基甲基)醚、聚(乙二醇)雙(3-乙基-3-氧呾基甲基)醚、二季戊四醇陸(3-乙基-3-氧呾基甲基)醚、二季戊四醇伍(3-乙基-3-氧呾基甲基)醚、二季戊四醇肆(3-乙基-3-氧呾基甲基)醚、經己內酯改質的二季戊四醇陸(3-乙基-3-氧呾基甲基)醚、經己內酯改質的二季戊四醇伍(3-乙基-3-氧呾基甲基)醚、二三羥甲基丙烷肆(3-乙基-3-氧呾基甲基)醚、經EO-改質的雙酚A雙(3-乙基-3-氧呾基甲基)醚、經PO-改質的雙酚A雙(3-乙基-3-氧呾基甲基)醚、經EO-改質之氫化的雙酚A雙(3-乙基-3-氧呾基甲基)醚、經PO-改質之氫化的雙酚A雙(3-乙基-3-氧呾基甲基)醚、和經EO改質的雙酚F(3-乙基-3-氧呾基甲基)醚。
這些陽離子可聚合的單體可以單獨使用或其二或更多類型併用。EO代表環氧乙烷。經EO-改質的化合物係具有環氧乙基的嵌段結構。PO代表環氧丙烷。PO-
改質的化合物係具有環氧丙基的嵌段結構。
(2)光聚合引發劑(組份B)
本發明之光可固化組成物中所含的光聚合引發劑(組份B)須根據作為組份A之可聚合單體的性質而適當地選擇。特定言之,在使用自由基可聚合的單體作為組份A的情況中,使用光自由基生成劑。或者,在使用陽離子可聚合的單體作為組份A的情況中,使用光酸生成劑。
(2-1)光自由基生成劑
光自由基產生劑是指曝於射線(如紅外光、可見光、紫外光、遠紅外光、X-射線)或帶電的粒子束(如電子束)會發生化學反應而形成引發自由基聚合反應所須之自由基的化合物。
此化合物的例子包括,但不限於,
經任意取代的2,4,5-三芳基咪唑二聚物,如2-(鄰-氯苯基)-4,5-二苯基咪唑二聚物、2-(鄰-氯苯基)-4,5-二(甲氧基苯基)咪唑二聚物、2-(鄰-氟苯基)-4,5-二苯基咪唑二聚物、和2-(鄰-或對-甲氧基苯基)-4,5-二苯基咪唑二聚物;二苯基酮衍生物,如二苯基酮、N,N’-四甲基-4,4’-二胺基二苯基酮(Michler氏酮)、N,N’-四乙基-4,4’-二胺基二苯基酮、4-甲氧基-4’-二甲胺基二苯基酮、4-氯二苯基酮、4,4’-二甲氧基二苯基酮、和4,4’-二胺基二苯基酮;芳族酮衍生物,如2-苄基-2-二甲胺基-1-(4-嗎啉基苯
基)-丁酮-1,2-甲基-1-[4-(甲硫基)苯基]-2-嗎啉基-丙-1-酮;醌,如2-乙基蒽醌、菲醌、2-三級丁基蒽醌、八甲基蒽醌、1,2-苯并蒽醌、2,3-苯并蒽醌、2-苯基蒽醌、2,3-二苯基蒽醌、1-氯蒽醌、2-甲基蒽醌、1,4-萘醌、9,10-菲醌、2-甲基-1,4-萘醌、和2,3-二甲基蒽醌;苯偶因醚衍生物,如苯偶因甲醚、苯偶因乙醚、和苯偶因苯醚;苯偶因衍生物,如苯偶因、甲基苯偶因、乙基苯偶因、和丙基苯偶因;苄基衍生物,如苄基二甲縮酮;吖啶衍生物,如9-苯基吖啶和1,7-雙(9,9’-吖啶基)庚烷;N-苯基甘胺酸衍生物,如N-苯基甘胺酸;苯乙酮衍生物,如苯乙酮、3-甲基苯乙酮、苯乙酮苄基縮酮、1-羥基環己基苯基酮、和2,2-二甲氧基-2-苯基苯乙酮;9-氧硫衍生物,如9-氧硫(thioxanthone)、二乙基-9-氧硫、2-異丙基-9-氧硫、和2-氯-9-氧硫;以及硫酮(xanthone)、茀酮(fluorenone)、苯甲醛、茀、蒽醌、三苯基胺、咔唑、1-(4-異丙基苯基)-2-羥基-2-甲基丙-1-酮、2-羥基-2-甲基-1-苯基丙-1-酮、2,4,6-三甲基苄醯基二苯基氧化膦、和雙-(2,6-二甲氧
基苄醯基)-2,4,4-三甲基戊基氧化膦。
前述化合物中,市售光自由基生成劑包括,
但不限於,Irgacure 184,369,651,500,819,907,784,和2959,CGI-1700,-1750,和-1850,CG24-61,和Darocur 1116和1173(皆由Ciba Japan Co.,Ltd.製造),Lucirin TPO,LR8893,和LR8970(皆由BASF製造),和Ubecryl P36(UCB製造)。
上列光自由基生成劑可以單獨使用或彼等的二或更多類型併用。
(2-2)光酸生成劑
該光酸生成劑是指是指曝於射線(如紅外光、可見光、紫外光、遠紅外光、X-射線)或帶電的粒子束(如電子束)會發生化學反應而形成引發陽離子聚合反應的酸(質子)之化合物。此化合物的例子包括,但不限於,鎓鹽化合物、碸化合物、磺酸酯化合物、磺醯亞胺化合物、和重氮甲烷化合物。本發明中,較佳地使用鎓鹽化合物。
鎓鹽化合物的例子包括可包括錪鹽、鋶鹽、鏻鹽、重氮鹽、銨鹽、和吡啶鹽。鎓鹽化合物的特定例子包括,但不限於,全氟-正丁磺酸雙(4-三級丁基苯基)錪、三氟丁烷酸雙(4-丁基苯基)錪、2-三氟甲基苯磺酸雙(4-三級丁基苯基)錪、芘磺酸雙(4-三級丁基苯基)錪、正十二烷基苯磺酸雙(4-三級丁基苯基)錪、對-甲苯磺酸雙(4-三級丁基苯基)錪、苯磺酸雙(4-三級丁基苯基)錪、10-樟腦磺
酸雙(4-三級丁基苯基)錪、正辛磺酸雙(4-第三丁基苯基)錪、全氟正丁磺酸二苯基錪、三氟甲磺酸二苯基錪、2-三氟甲基苯磺酸二苯基錪、芘磺酸二苯基錪、正十二烷基苯磺酸二苯基錪、對-甲苯磺酸二苯基錪、苯磺酸二苯基錪、10-樟腦磺酸二苯基錪、正辛磺酸二苯基錪、全氟正丁磺酸三苯基鋶、三氟甲磺酸三苯基鋶、2-三氟甲基苯磺酸三苯基鋶、芘磺酸三苯基鋶、正十二烷基苯磺酸三苯基鋶、對-甲苯磺酸三苯基鋶、苯磺酸三苯基鋶、10-樟腦磺酸三苯基鋶、正辛磺酸三苯基鋶、全氟正丁磺酸二苯基(4-三級丁基苯基)鋶、三氟甲磺酸二苯基(4-三級丁基苯基)鋶、2-三氟甲基苯磺酸二苯基(4-三級丁基苯基)鋶、芘磺酸二苯基(4-三級丁基苯基)鋶、正十二烷基苯磺酸二苯基(4-三級丁基)鋶、對-甲苯磺酸二苯基(4-三級丁基苯基)鋶、苯磺酸二苯基(4-三級丁基苯基)鋶、10-樟腦磺酸二苯基(4-三級丁基苯基)鋶、正辛磺酸二苯基(4-三級丁基苯基)鋶、全氟正丁磺酸參(4-甲氧基苯基)鋶、三氟甲磺酸參(4-甲氧基苯基)鋶、2-三氟甲基苯磺酸參(4-甲氧基苯基)鋶、芘磺酸參(4-甲氧基苯基)鋶、正十二烷基苯磺酸參(4-甲氧基苯基)鋶、對-甲苯磺酸參(4-甲氧基苯基)鋶、
苯磺酸參(4-甲氧基苯基)鋶、10-樟腦磺酸參(4-甲氧基苯基)鋶、和正辛磺酸參(4-甲氧基苯基)鋶。
碸化合物的例子可包括,β-酮基碸、β-磺醯基碸、和彼等的α-重氮化合物。碸化合物的特定例子包括,但不限於,苯甲醯苯基碸、2,4,6-三甲苯基苯甲醯甲基碸、雙(苯基磺醯基)甲烷、和4-參苯甲醯甲基碸。
磺酸酯化合物的例子可包括,但不限於,烷基磺酸酯、鹵烷基磺酸酯、芳基磺酸酯、和亞胺基磺酸酯。磺酸酯化合物的特定例子包括,但不限於,α-羥甲基苯偶因全氟正丁磺酸酯、α-羥甲基苯偶因三氟甲磺酸酯、和α-羥甲基苯偶因2-三氟甲基苯磺酸酯。
磺醯亞胺化合物的特定例子包括,但不限於,N-(三氟甲基磺醯氧基)丁二.醯亞胺、N-(三氟甲基磺醯氧基)酞醯亞胺、N-(三氟甲基磺醯氧基)二苯基馬來醯亞胺、N-(三氟甲基磺醯氧基)二環[2.2.1]庚-5-烯-2,3-二羧醯亞胺、N-(三氟甲基磺醯氧基)-7-氧二環[2.2.1]庚-5-烯-2,3-二羧醯亞胺、N-(三氟甲基磺醯氧基)二環[2.2.1]庚-5,6-氧-2,3-二羧醯亞胺、N-(三氟甲基磺醯氧基)萘醯亞胺、N-(10-樟腦磺醯氧基)丁二醯亞胺、N-(10-樟腦磺醯氧基)酞醯亞胺、N-(10-樟腦磺醯氧基)二苯基馬來醯亞胺、N-(10-樟腦磺醯氧基)二環[2.2.1]庚-5-烯-2,3-二羧醯亞胺、N-(10-樟腦磺醯氧基)-7-氧雜二環[2.2.1]庚-5-烯-2,3-二羧醯亞胺、N-(10-樟腦磺醯氧基)二環[2.2.1]庚-5,6-氧-2,3-二羧
醯亞胺、N-(10-樟腦磺醯氧基)萘醯亞胺、N-(4-甲基苯基磺醯氧基)丁二醯亞胺、N-(4-甲基苯基磺醯氧基)酞醯亞胺、N-(4-甲基苯基磺醯氧基)二苯基馬來醯亞胺、N-(4-甲基苯基磺醯氧基)二環[2.2.1]庚-5-烯-2,3-二羧醯亞胺、N-(4-甲基苯基磺醯氧基)-7-氧二環[2.2.1]庚-5-烯-2,3-二羧醯亞胺、N-(4-甲基苯基磺醯氧基)二環[2.2.1]庚-5,6-氧-2,3-二羧醯亞胺、N-(4-甲基苯基磺醯氧基)萘醯亞胺、N-(2-三氟甲基苯基磺醯氧基)丁二醯亞胺、N-(2-三氟甲基苯基磺醯氧基)酞醯亞胺、N-(2-三氟甲基苯基磺醯氧基)二苯基馬來醯亞胺、N-(2-三氟甲基苯基磺醯氧基)二環[2.2.1]庚-5-烯-2,3-二羧醯亞胺、N-(2-三氟甲基苯基磺醯氧基)-7-氧雜二環[2.2.1]庚-5-烯-2,3-二羧醯亞胺、N-(2-三氟甲基苯基磺醯氧基)二環[2.2.1]庚-5,6-氧-2,3-二羧醯亞胺、N-(2-三氟甲基苯基磺醯氧基)萘醯亞胺、N-(4-氟苯基磺醯氧基)丁二醯亞胺、N-(4-氟苯基磺醯氧基)酞醯亞胺、N-(4-氟苯基磺醯氧基)二苯基馬來醯亞胺、N-(4-氟苯基磺醯氧基)二環[2.2.1]庚-5-烯-2,3-二羧醯亞胺、N-(4-氟苯基磺醯氧基)-7-氧雜二環[2.2.1]庚-5-烯-2,3-二羧醯亞胺、N-(4-氟苯基磺醯氧基)二環[2.2.1]庚-5,6-氧-2,3-二羧醯亞胺、和N-(4-氟苯基磺醯氧基)萘醯亞胺。
重氮甲烷化合物的特定例子包括,但不限於,雙(三氟甲基磺醯基)重氮甲烷、雙(環己基磺醯基)重氮甲烷、雙(苯基磺醯基)重氮甲烷、雙(對-甲苯磺醯基)重氮甲烷、甲基磺醯基對-甲苯磺醯基重氮甲烷、(環己基磺
醯基)(1,1-二甲基乙基磺醯基)重氮甲烷、和雙(1,1-二甲基乙基磺醯基)重氮甲烷。
這些光酸生成劑中,較佳者係鎓鹽化合物。本發明中,上列光酸生成劑可以單獨使用或彼等的二或更多類型併用。
相對於本發明之光聚合組成物中所含可聚合單體(組份A)的總量,光聚合引發劑(B)組份的摻合比為0.01重量%或更多且10重量%或更少,較佳地為0.1重量%或更多且7重量%或更少。若摻合比低於0.01重量%,則所得的光可固化組成物會因為固化速率降低而具有低反應效率。若摻合比超過10重量%,則所得用於光壓印之光可固化組成物的固化產物之機械特性欠佳。
(3)含氟原子的界面活性劑(組份C)
較佳地,本發明之光可固化組成物應含有含氟原子的界面活性劑。在下文描述的光固化產物製造期間內,該含氟原子的界面活性劑以薄膜形式分佈於光固化產物和模具之間的界面。含氟原子的界面活性劑作為光固化產物的一種塗覆材料。此處,含氟原子的界面活性劑所含氟原子造成表面能量降低。認為製造光固化產物時,光固化產物自模具脫離所須的脫模力可藉此效應而降低。
本發明之光可固化組成物中所含之含氟原子的界面活性劑較佳地為具有環氧乙基(-CH2CH2O-)的化合物,更佳地為以下式[1]代表的化合物:
R1-x1-R2-x2-R3 [1]
式[1]中,R1代表全氟烷基。R1所代表的全氟烷基的特定例子包括具有2至20個碳原子且氟原子代替所有氫原子的烷基,如全氟乙基、全氟丙基、全氟丁基、全氟戊基、全氟己基、全氟庚基、全氟辛基、全氟壬基、和全氟癸基。就環境安全的觀點,全氟烷基中的碳原子數可為7或更低。
式[1]中,R2代表含有環氧乙基的二價取代基。此處,該含有環氧乙基的二價取代基特定地為以下的二價取代基(i)或(ii):(i)含有環氧乙基的聚環氧乙烷鏈;和(ii)含有環氧乙基的烷基鏈。
二價取代基(i)的特定例子包括具1至100個重覆單元的聚環氧乙烷鏈和具1至100個重覆單元的聚環氧丙烷鏈(-CH2CH(CH3)O-)。
二價取代基(ii)的特定例子包括具有具1至100個重覆單元的聚環氧乙烷鏈和具2至100個碳原子的直鏈烷基之聚合物鏈,及具有具1至100個重覆單元的聚環氧丙烷鏈和含有環狀結構的烷基之聚合物鏈。
式[1]中,R3代表極性官能基。R3代表的極性官能基包括烷羥基、羧基、巰基、吡啶基、矽醇基、和磺酸基。
式[1]中,x1和x2各自代表單鍵或二價取代基。x1或x2是二價取代基的情況中,其特定例子包括伸烷基、伸苯基、伸萘基、酯、醚、硫醚、磺醯基、二級胺基、三級胺基、醯胺、和胺甲酸酯基。
這些含氟原子的界面活性劑可以單獨使用或其二或更多類型併用。
本發明之光固化組成物中所含之含氟原子的界面活性劑的摻合比由光可固化組成物中所含可聚合單體(組份A)的總量決定。特定言之,以組份A總量計,此摻合比為0.001重量%至5重量%,較佳地為0.002重量%至4重量%,更佳地為0.005重量%至3重量%。
(額外組份)
根據各種目的,除了前述可聚合的單體(組份A)、光聚合引發劑(組份B)、和含氟原子的界面活性劑(組份C)以外,本發明之光可固化組成物可以未損及本發明之效果地含有額外組份。此處,額外組份為特定組份,如敏化染料、抗氧化物、溶劑、和聚合物組份。此處,將描述其個別的特定例子。
(敏化染料)
本發明之光可固化組成物可含有敏化染料以促進聚合反應或改良反應轉化率。可於其中添加氫供給體或敏化染料作為敏化染料。
此氫供給體是指與自光聚合引發劑(組份B)形成之引發用的自由基或散播端的自由基反應而形成更具反應性的自由基之化合物。此氫供給體可於光聚合引發劑(組份B)係光自由基生成劑的情況中添加。
目前已知常用的化合物可作為氫供給體。特定言之,其例子包括,但不限於,胺化合物,如N-丁胺、二正丁胺、三正丁膦、烯丙烯硫脲、二級苯甲基異秋蘭姆-對-甲苯亞磺酸鹽、三乙胺、甲基丙烯酸二甲胺基乙酯、三伸乙四胺、4,4’-雙(二烷胺基)二苯基酮、N,N-二甲胺基苯甲酸乙酯、N,N-二甲胺基苯甲酸異戊酯、戊基-4-二甲胺基苯甲酸酯、三乙醇胺、和N-苯基甘胺酸;和巰基化合物,如2-巰基-N-苯基苯并咪唑和巰基丙酸酯。
敏化染料是指具有藉由吸收具有特別波長的光而激發以誘發與光聚合引發劑(組份B)之交互作用之性質的化合物。此處,此交互作用特定地含括自處於激發態的敏化染料能量轉移、電子轉移之類。
目前已知的常用化合物可作為敏化染料。特定言之,其包括,但不限於,蒽衍生物、蒽醌衍生物、芘衍生物、苝衍生物、咔唑衍生物、苯乙酮衍生物、9-氧硫衍生物、硫酮衍生物、9-氧硫衍生物、香豆素衍生物、啡噻(phenothiazine)衍生物、樟腦醌衍生物、吖啶衍生物、硫代吡喃鎓鹽(thiopyrylium salt)染料、部花青素(merocyanine)染料、喹啉染料、苯乙烯基喹啉染料、酮基香豆素染料、硫代(thioxanthene)染料、
(xanthene)染料、oxonol染料、靛青(cyanine)染料、玫紅(rhodamine)染料、和吡喃鎓鹽染料。
這些敏化染料可以單獨使用或其二或更多類型併用。相對於作為組份A之可聚合單體的總量,敏化染料在本發明中之光固化組成物中的含量較佳地為0至20重量%,更佳地為0.1重量%至5.0重量%,又更佳地為0.2重量%至2.0重量%。此處,敏化染料含量為0.1重量%或更高時,可有效地得到其效果。敏化染料含量為5重量%或更低時,光固化產物亦可具有夠高的分子量,且可防止溶解度欠佳或儲存安定性受損。
(摻合各組份之方法)
本發明之光可固化的組成物可藉由混合前述組份而製得。此處,混合和溶解光可固化組成物之組份的溫度條件通常在0℃至100℃的範圍內。溶劑可用以製造該光可固化組成物。此處,未特別限制製造光可固化組成物所用溶劑,只要溶劑不會造成與可聚合的單體之相分離即可。
(組成物之黏度)
本發明之光可固化組成物之黏度於無溶劑的23℃黏度較佳地在1至100 cP的範圍內,更佳地為5至50 cP,又更佳地為6至20 cP。光可固化組成物的黏度超過100 cP,則在與模具接觸時以組成物填充模具上的精細圖案之下凹部分所須時間較長或者會因為填充不良而造成圖案缺
陷。反之,光可固化組成物的黏度低於1 cP則會造成塗覆期間的分佈不均或者會在與模具接觸時,自模具端漏出。
(組成物之表面張力)
本發明之光可固化組成物於無溶劑的23℃表面張力較佳地在5毫牛頓/米至70毫牛頓/米的範圍內,更佳地為7毫牛頓/米至35毫牛頓/米,又更佳地為10毫牛頓/米至32毫牛頓/米。此處,當與模具接觸時,表面張力低於5毫牛頓/米的光可固化組成物以組成物填充模具上的精細圖案之下凹部分所須時間較長。反之,表面張力高於70毫牛頓/米的光可固化組成物之表面平滑度低。
(雜質)
希望儘可能地自本發明之光可固化組成物移除雜質。例如,該光可固化組成物可經混合並於之後濾經,例如,孔尺寸為0.001微米至5.0微米的濾器以避免粒子污染光可固化組成物而造成光固化產物的圖案缺陷。使用濾器之過濾可以多階段進行或重覆數次。或者,濾液可再度經過濾。製自聚乙烯樹脂、聚丙烯樹脂、氟樹脂、尼龍樹脂之類的濾器可用於過濾,但濾器不限於此。
在使用本發明之光可固化組成物製造半導體積體電路的情況中,可儘量降低組成物被金屬雜質污染的程度以免限制產物之操作。此處,本發明之光可固化組成
物中所含金屬雜質濃度較佳地為10 ppm或更低,更佳地為100 ppb或更低。
製造光固化產物之方法
之後將描述製造光固化產物之方法。
圖1A至1F各者為截面圖,其以圖說明製造本發明之光固化產物的方法之製法的一個例子。本發明之光固化產物係根據圖1A至1F中所示的製法(即,下文所示的步驟(i)至(v))製得。本發明之方法至少包括以下所示的步驟(i)至(iv)。用於光固化產物之確實製造,製造含有可聚合單體和含氟原子的界面活性劑之光可固化組成物之步驟(光可固化組成物製造步驟)係於步驟(i)(塗膜形成步驟)之前進行:(i)以光可固化組成物塗覆基板以形成塗膜的步驟(塗膜形成步驟;圖1A);(ii)令塗膜與模具接觸的步驟(壓印步驟;圖1B和1C);(iii)以光經由模具照射該光可固化組成物的步驟(照光步驟;圖1D);(iv)該經光照射以在基板上形成預定圖案之塗膜自模具脫模的步驟(脫模步驟;圖1E);和(v)移除留在圖案形狀中應移除塗膜之區域中之殘留膜的步驟(殘留膜移除步驟;步驟1F)。
下文中將詳細描述步驟(i)至(v)。製造本發明之光固化產物的方法係使用光的奈米壓印法。此外,藉本
發明之製法製得的膜所具有的圖案尺寸較佳地為1奈米至10毫米,更佳地約10奈米至100微米。
(1)塗膜形成步驟
首先,進行以光可固化組成物塗覆基板以形成塗膜的步驟(塗膜形成步驟)。此步驟(塗膜形成步驟)中,如圖1A所示者,可固化組成物製的塗膜(即,圖案複製層1)形成於基板材料(基板2)上。
通常使用矽晶圓作為基板材料,但基板材料不限於此。代替矽晶圓,基板材料可以任意地選自已知用於半導體裝置之製自鋁、鈦-鎢合金、鋁-矽合金、鋁-銅-矽合金、氧化矽、氮化矽之類者。所用的該基板(基板材料)可經表面處理,例如,藉矽烷偶合處理、矽氮烷處理、或薄有機膜形成,藉此改良基板與光可固化組成物之黏著性。
例如,可藉噴墨法、浸塗法、氣刀塗覆法、簾塗法、線棒塗覆法(wire bar coating)、照相凹版印刷塗覆法、壓出塗覆法、旋塗法、或縫隙掃描法(slit scanning method)以光可固化組成物塗覆基板材料。圖案複製層(塗膜)的膜厚度取決於產物之用途而不同且是,例如,0.01至100.0微米。
(2)壓印步驟
之後,進行令先前步驟(塗膜形成步驟)中形成的塗膜
與模具接觸的步驟(壓印步驟;圖1B和1C)。此步驟(壓印步驟)中,模具3與圖案複製層1接觸(圖1B),使得形成於模具3上之精細圖案的下凹部分經(一部分的)塗膜10填補(圖1C)。
考慮後續步驟(照光步驟),接觸步驟中使用的模具3須製自透光材料。構成模具的材料的例子特定地包括玻璃、石英、透光樹脂(如PMMA或聚碳酸酯樹脂)、透明的蒸鍍金屬膜、軟膜(如聚二甲基矽氧烷膜)、光固化膜、和金屬膜。使用透光樹脂作為模具的構成材料時,須選擇不溶於光可固化組成物1中所含溶劑的樹脂。
製造本發明之光固化產物之方法中所用的模具3可經表面處理以改良光可固化組成物1和模具3表面之間的脫模性。此表面處理法可為以聚矽氧或氟矽烷偶合劑處理或可以特定地使用市售的塗料型脫模劑,如Daikin Industries,Ltd.生產的Optool DSX。
接觸步驟中,如圖1B所示者,當模具3與圖案複製層1接觸時,未特別限制施於圖案複製層1的壓力,且通常為0.1 MPa至100 MPa。特別地,較佳為0.1 MPa至50 MPa,更佳為0.1 MPa至30 MPa,又更佳為0.1 MPa至20 MPa。此外,此接觸步驟中,未特別限制模具3與圖案複製層1的接觸期間且通常為1秒至600秒,較佳地為1秒至300秒,更佳地為1秒至180秒,特別佳地為1秒至120秒。
此接觸步驟可以在選自在大氣中、在減低壓
力下、和在惰性氣體中的條件下進行。在惰性氣體中進行壓印步驟時,所用惰性氣體的特定例子包括氮、一氧化碳、氦、氬、各種氯氟化碳氣體、和其氣體混合物。
(3)照光步驟
之後,進行以光經由模具照射塗膜的步驟(照光步驟;圖1C)。此步驟中,塗膜藉照光而固化形成光固化產物11。
此處,照射圖案複製層1的光係根據光可固化組成物的敏感性波長選擇並可特定地適當地選自紫外光、X-射線、電子束等波長約150奈米至400奈米者。此處,許多市售的光聚合引發劑(組份B)係對於紫外光敏感的化合物。因此,照射圖案複製層1的光(照射光4)特別佳地為紫外光。此處,紫外光的光源的例子包括高壓汞燈、超高壓汞燈、低壓汞燈、深UV燈、碳弧燈、化學燈、金屬鹵素燈、氙燈、KrF準分子雷射、ArF準分子雷射、和F2準分子雷射。特別佳者係超高壓汞燈。所用光源的數目可為一或可為二或更多。此照光可施於圖案複製層1的全表面或可以僅施於其部分區域。
或者,圖案複製層可藉熱固化。此情況中,可進一步進行熱固化。熱固化時,未特別限制加熱的氣氛和溫度等。例如,圖案複製層1可於40℃至200℃的溫度範圍在惰性氣氛或在減低的壓力下加熱。此外,圖案複製層1可以使用加熱盤、烘箱、爐之類加熱。
(4)脫模步驟
之後,光可固化組成物自模具脫離而在基板上形成具有預定圖形狀的膜(脫模步驟;圖1E)。此步驟(脫模步驟)係圖案複製層自模具脫離的步驟,藉此,得到精細圖案的相反圖案形成於模具上,其為在先前步驟(照光步驟)中固化的光可固化組成物中之圖案。
未特別限制固化的圖案複製層(固化膜11)自模具3脫模的方法,只要脫模法不會以物理方式損及固化膜11的部分即可。類似地,未特別限制各種條件等。例如,固定基板材料(基板2),此模具3可自基板材料移開,藉此而脫模。或者,固定模具3,自模具移開基板材料,藉此而脫模。或者,模具3和基板材料朝相反方向拉開,藉此而脫模。
同樣地,可以藉由採取使用塗覆型脫模劑的方法,模具3自固化膜11脫模。此處,使用塗覆型脫模劑使得固化膜11自模具3脫離時,在壓印步驟之前,進行在具有所欲圖案的模具表面上形成塗覆型脫模劑層的步驟。
所用塗覆型脫模劑的類型的例子包括,但未特別限於,矽脫模劑、氟脫模劑、聚乙烯脫模劑、聚丙烯脫模劑、烷烴脫模劑、褐煤蠟(montan)脫模劑、和棕櫚蠟(carnauba)脫模劑。這些脫模劑可以單獨使用或其二或更多類型併用。這些脫模劑中,氟脫模劑為特別佳者。
(5)殘留膜移除步驟
藉脫模步驟得到膜具有特別的圖案形狀。但是,膜的一部分以殘留膜的形式存在於具有此圖案形狀的區域以外的區域。因此,進行移除圖案形狀中之光可固化組成物應被移除之區域之光可固化組成物(殘留膜)的步驟(殘留膜移除步驟;圖1F)。
此處,移除殘留膜之方法的例子包括含括移除留在圖案複製層的下凹部分中之膜(殘留膜)之方法,此藉由蝕刻而使得圖案的下凹部分處的基板材料表面外露。
未將所用蝕刻特別限制於特定方法,且可進行以前已知的方法,例如,乾蝕法。以前已知的乾蝕設備可用於乾蝕法。根據待蝕刻的膜之元素組成,適當地選擇用於乾蝕的來源氣體。例如,可以使用含氧原子的氣體(如氧O2、CO、或CO2)、惰性氣體(如He、N2或Ar)、氯氣(如Cl2或BCl3)或任何其他氣體(如H2或NH3)。這些氣體可經混合使用。
具有藉前述光奈米壓印法形成之圖案的膜可以作為,例如,半導體裝置(如LSI、系統LSI、DRAM、SDRAM、RDRAM、或D-RDRAM)的層間絕緣體的膜,或製造半導體裝置的光阻膜。
特定言之,根據以下具體實施例,本發明提供使用前述具體實施例的光可固化組成物之方法。
本發明提供使用具有上凸/下凹表面之模具在
固化產物中形成圖案之方法及製造具有圖案的固化產物之方法。
本發明亦提供製造電路基板(如半導體裝置)之方法,製造電路基板之方法,包含:將光可固化組成物施於基材上;令模具壓於光可固化組成物以在光可固化組成物中形成圖案;以光照射具有圖案的光可固化組成物以製造具有圖案的固化產物;和固化產物自模具脫模而在基材上形成以固化產物中的圖案為基礎之電路結構。
實例
下文中,將藉以下實例更詳細地描述本發明。但本發明不限於以下所述實例。以下的描述中,除非特定指明,否則“份”是指“重量份”。除非特定指明,否則“%”是指“重量%”。
[合成例1]含氟原子的界面活性劑(C-1)之合成
(1)300毫升反應器中維持於氮環境時,以下試劑和溶劑加至此反應器中:六乙二醇(PEG6):26.5克(93.9毫莫耳,1.0當量)
四氯化碳(CCl4):36.1克(235毫莫耳,2.5當量)
四氫呋喃(THF):106毫升
之後,反應溶液冷卻至-30℃。之後,以THF(24毫升)稀釋的二甲胺基膦(15.3克,93.9毫莫耳,1.0當量)以2小時逐漸地添加至此反應溶液中,此混合物
於此溫度攪拌30分鐘。之後,反應器自冷卻浴移出,此反應溶液於室溫攪拌2小時。之後,在此反應溶液(淡黃色懸浮液)中添加自來水(250毫升)以將反應溶液分離成兩層(CCl4層和含水層)。接著,收集含水層。之後,此含水層以異丙醚(IPE)(150毫升)清洗兩次。之後,藉由將六氟磷酸鉀(KPF6)(34.5克,188毫莫耳,2.0當量)分散於自來水(250毫升)中製得懸浮液並將其加至含水層中,之後充分攪拌此混合物。然後,使用二氯甲烷(200毫升)三度進行溶劑萃取操作。合併有機層,以自來水(400毫升)和飽和鹽水(300毫升)依序清洗,並以無水硫酸鎂加以乾燥。之後,有機層在減低壓力下濃縮以得到53克淡棕色液體(下文中稱為組份"C-1-a")。
(2)以下試劑和溶劑加至500毫升反應器中:1H,1H-全氟-1-庚醇:34.2 g(97.7毫莫耳,1.2當量)THF:120毫升
之後,60% NaH(3.9克,97.7毫莫耳,1.2當量)逐漸加至此反應溶液中,且反應溶液未起泡。之後,此反應溶液加熱至50℃並於此溫度(50℃)攪拌1小時。之後,溶劑於減低壓力下蒸除。於所得殘渣中,添加溶於無水二噁烷(600毫升)的組份C-1-a(53克)。之後,反應溶液加熱至60℃並於此溫度(60℃)攪拌48小時。然後,處於懸浮態的反應溶液於減低壓力下濃縮。自來水(300毫升)和乙酸乙酯(300毫升)加至所得殘渣中,藉溶劑萃取操作收集有機層。然後,含水層以乙酸乙酯(200毫升)二度進
行溶劑萃取,所得的有機層與先前收集的有機層合併。然後,此有機層以自來水(400毫升)和飽和鹽水(400毫升)依序清洗並於之後以無水硫酸鎂加以乾燥。然後,有機層在減低壓力下濃縮而得到59.1克棕色液體。此棕色液體藉管柱層析法純化(填充材料:SiO2(1.2公斤),沖提溶劑:僅乙酸乙酯→乙酸乙酯/甲醇=10/1)。然後,經純化的產物進一步藉管柱層析法純化(填充材料:SiO2(400克),沖提溶劑:氯仿/甲醇=15/1→10/1)。然後,經純化的產物在高真空下乾燥。以此方式,得到19.2克(31.2毫莫耳,產率33%)含氟原子的界面活性劑F(CF2)6CH2(OCH2CH2)6OH作為組份C-1,其為無色液體。
[合成例2]含氟原子的界面活性劑(C-2)之合成
(1)100毫升反應器內部維持氮環境時,以下試劑和溶劑加至此反應器中:六丙二醇(P400):20克(50毫莫耳,1.0當量)
四氯化碳(CCl4):19.2克(125毫莫耳,2.5當量)
四氫呋喃(THF):100毫升
之後,反應溶液冷卻至-30℃。之後,以THF(30毫升)稀釋的二甲胺基膦(8.16克,10毫莫耳,1.0當量)以2小時逐漸地添加至此溶液中,此混合物於相同溫度攪拌30分鐘。之後,反應器自冷卻浴移出,此反應溶液於室溫攪拌2小時。然後,在此反應溶液(淡黃色懸
浮液)中添加自來水(350毫升)以將反應溶液分離成兩層(CCl4層和含水層)。之後,收集含水層。然後,此含水層以異丙醚(IPE)(150毫升)清洗兩次。之後,藉由將六氟磷酸鉀(18.4克,100毫莫耳,2.0當量)分散於自來水(250毫升)中製得懸浮液並將其加至含水層中,之後充分攪拌此混合物。然後,使用二氯甲烷(150毫升)三度進行溶劑萃取操作。合併有機層,以自來水(500毫升)和飽和鹽水(300毫升)依序清洗,並以無水硫酸鎂加以乾燥。之後,有機層在減低壓力下濃縮以得到31克淡棕色液體(下文中稱為組份"C-2-a")。
(2)以下試劑和溶劑加至500毫升反應器中:1H,1H-全氟-1-庚醇:21 g(60毫莫耳,1.2當量)THF:120毫升
之後,60% NaH(3.9克,97.7毫莫耳,1.2當量)逐漸加至此反應溶液中,且反應溶液未起泡。之後,此反應溶液加熱至40℃並於此溫度(40℃)攪拌1小時。之後,溶劑於減低壓力下蒸除。於所得殘渣中,添加溶於無水二噁烷(350毫升)的組份C-2-a(31克)。之後,反應溶液加熱至60℃並於此溫度(60℃)攪拌24小時。然後,處於懸浮態的反應溶液於減低壓力下濃縮。自來水(200毫升)和乙酸乙酯(200毫升)加至所得殘渣中,藉溶劑萃取操作收集有機層。然後,含水層以乙酸乙酯(150毫升)二度進行溶劑萃取,所得的有機層與先前收集的有機層合併。然後,此有機層以自來水(500毫升)和飽和鹽水(500毫升)依
序清洗並於之後以無水硫酸鎂加以乾燥。然後,有機層在減低壓力下濃縮而得到29克棕色液體。此棕色液體藉管柱層析法純化(填充材料:SiO2(0.9公斤),沖提溶劑:乙酸乙酯/乙烷=2/1→僅乙酸乙酯)。然後,經純化的產物進一步藉管柱層析法純化(填充材料:SiO2(300克),沖提溶劑:氯仿/甲醇=20/1→10/1)。然後,經純化的產物在高真空下乾燥。以此方式,得到1.71克(2.78毫莫耳,產率14%)含氟原子的界面活性劑F(CF2)6CH2(OCH2C2H4)6OH作為組份C-2,其為無色液體。
實例1
(1)光可聚合組成物之製造
首先,混合以下試劑和溶劑:(組份A)丙烯酸異酯(Kyoeisha Chemical Co.,Ltd.製造):62重量份
(組份A)二丙烯酸1,6-己二醇酯(Osaka Organic Chemical Industry Ltd.製造):22重量份
(組份A)Medol 10(Osaka Organic Chemical Industry,Ltd.製造):16重量份
(組份B)Irgacure 369(Ciba Japan Co.,Ltd.製造):3重量份(組份C-1)含氟原子的界面活性劑(F(CF2)6CH2(OCH2CH2)6OH):2重量份
之後,組份A、B和C-1的混合溶液濾經四氟乙烯製的0.2微米濾器以得到此實例(實例1)的光可固化
組成物(a-1)。
使用自動表面張力計CBVP-A3(Kyowa Interface Science Co.,Ltd.製造)測定所得光可固化組成物的表面張力,測定結果為23.9毫牛頓/米。亦使用旋轉式錐-板黏度計RE-85L(Toki Sangyo Co.,Ltd.製造)測定所得光可固化組成物的黏度,測定結果為6.95 cP。
(2)光固化產物之製造
(2-1)成膜步驟
使用微滴管,將15微升光可固化組成物(a-1)逐滴加於4英吋矽晶圓上以形成膜。此處,作為黏著層之用的黏著促進層以60奈米厚度形成於矽晶圓上。
(2-2)接觸步驟
之後,未經表面處理亦無圖案的40毫米×40毫米石英模具置於矽晶圓上並與光可固化組成物(a-1)接觸。
(2-3)照光步驟
之後,與石英模具接觸的光可固化組成物(a-1)以光照射60秒。所用照射設備為UV light source EXECURE 3000(Hoya Candeo Optronics Corporation製造),其配備200瓦汞氙燈作為照射光源。此外,干擾濾器VPF-50C-10-25-36500(Sigma Koki Co.,Ltd.製造)置於照射光源和石英模具之間。緊鄰石英模具的照度為1毫瓦特/平方米,
波長為365奈米。
(2-4)脫模步驟
之後,石英模具以0.5毫米/秒的條件上提以使石英模具與光可固化組成物製的固化膜(光固化產物)分離。以此方式,得到光固化產物。
(3)光固化產物之評估
(3-1)脫模力之測定
此處,使用衝擊張力/壓縮計力器LUR-A-200NSA1(Kyowa Electronic Instruments Co.,Ltd.製造),測定在脫模步驟中,石英模具與光固化產物分離(脫模)所須的力,即,脫模力。在相同條件下,四度測定脫模力,計算第二和第四次測定的平均值作為此實例的脫模力。其結果示於表1。
(3-2)TOF-SIMS測定
此實例中所得之光固化產物的表面進行TOF-SIMS測定。此TOF-SIMS測定使用ION-TOF GmbH製造的TOF-SIMS V設備。測定條件設定如下:原始離子:Bi3 +,0.3 pA(脈衝電流值)
鋸齒掃描模式中的原始離子脈衝頻率:10 kHz(100微秒/扇區脈衝)
原始離子脈衝寬度:約0.8毫微秒
測定面積:500微米×500微米
測定面積中之像素數目:128×128
掃描數:32
二次離子偵測模式:positive
用於中和的注射器:ON
用於TOF-SIMS測定,一個樣品任意地設定3個測定點並測定各者。之後,計算於各測定點得到的質譜峰面積作為訊號強度。計算各個峰的訊號強度之平均。計算結果示於以下的表1。
實例2
(1)光可固化組成物之製造
以與實例1相同的方式製造此實例(實例2)的光可固化組成物(a-2),但作為實例(1)中之組份C-1之含氟原子的化合物(F(CF2)6CH2(OCH2CH2)6OH)的摻合量改為0.5重量份。
以與實例1相同的方式測定光可固化組成物(a-2)的表面張力,測定結果為27.5毫牛頓/米。亦以與實例1相同的方式測定光可固化組成物(a-2)的黏度,測定結果為6.77 cP。
(2)光固化產物之製造
以與實例1相同的方式製造光固化產物,但使用光可固化組成物(a-2)代替實例1的光可固化組成物(a-1)。亦以
與實例1中相同的方式進行脫模力測定和TOF-SIMS測定。其結果示於表1。
比較例1
(1)光可固化組成物之製造
首先,混合以下試劑和溶劑:
(組份A)二丙烯酸1,6-己二醇酯(Osaka Organic Chemical
Industry,Ltd.製造):100重量份
(組份B)Irgacure 369(Ciba Japan Co.,Ltd.製造):3重量份
(組份C-2)含氟原子的界面活性劑:2重量份
之後,組份A、B和C-2的混合溶液濾經四氟乙烯製的0.2微米濾器以得到此比較例(比較例1)的光可固化組成物(b-1)。
以與實例1相同的方式測得此光可固化組成物(b-1)的表面張力,測定結果為19.5毫牛頓/米。亦以與實例1相同的方式測定光可固化組成物(b-1)的黏度,測定結果為6.45 cP。
(2)光固化產物之製造
以與實例1相同的方式製造光固化產物,但使用光可固化組成物(b-1)代替實例1的光可固化組成物(a-1)。亦以與實例1中相同的方式進行脫模力測定和TOF-SIMS測定。其結果示於表1。
實例1與比較例1之比較證實,儘管含氟原子的界面活性劑的含量相同,實例1之光固化產物所須的脫模力小於比較例1所須者。實例1中,C2H5O+離子(m/z=45)的訊號強度高於C3H7O+離子(m/z=59)的訊號強度。反之,比較例1中,C2H5O+離子(m/z=45)的訊號強度低於C3H7O+離子(m/z=59)的訊號強度。
實例2與比較例1之比較證實,儘管實例2中之含氟原子的界面活性劑的含量低於比較例1中之含量,實例2之光固化產物所須的脫模力小於比較例1所須者。實例2中的光固化產物中,C2H5O+離子(m/z=45)的訊號強度高於C3H7O+離子(m/z=59)的訊號強度,此與實例1相同。
比較例2
以與實例1相同的方式製造光可固化組成物(c-1),但其中未含有實例1之製造光可固化組成物中所含之含氟原子的界面活性劑(組份C-1)。
以與實例1相同的方式測得此光可固化組成
物(c-1)的表面張力,測定結果為31.2毫牛頓/米。亦以與實例1相同的方式測定光可固化組成物(c-1)的黏度,測定結果為6.80 cP。
以與實例1相同的方式製造光固化產物,但使用光可固化組成物(c-1)代替實例1的光可固化組成物(a-1)。亦以與實例1中相同的方式進行脫模力測定且測定結果為157毫牛頓/米。
這些結果證實自沒有含氟原子的界面活性劑之光可固化組成物(如同比較例2)製得的光固化產物所須的脫模力大於自含有含氟原子的界面活性劑之光可固化組成物製得者所須者。
比較例3
以與比較例1相同的方式製造光可固化組成物(c-2),但其未含有比較例1之製造光可固化組成物中所含之含氟原子的界面活性劑(組份C-2)。
以與實例1相同的方式測得此光可固化組成物(c-2)的表面張力,測定結果為35.9毫牛頓/米。亦以與實例1相同的方式測定光可固化組成物(c-2)的黏度,測定結果為6.34 cP。
以與比較例1相同的方式製造光固化產物,但使用光可固化組成物(c-2)代替比較例1的光可固化組成物(b-1)。亦以與實例1中相同的方式進行脫模力測定且測定結果為158毫牛頓/米。
這些結果證實自沒有含氟原子的界面活性劑之光可固化組成物(如同比較例3)製得的光固化產物所須的脫模力大於自含有含氟原子的界面活性劑之光可固化組成物製得者所須者。
前述結果證實藉TOF-SIMS得知C2H5O+離子(m/z=45)的訊號強度高於C3H7O + 離子(m/z=59)的訊號強度之含有含氟原子的界面活性劑之光可固化組成物僅須小脫模力。
前述結果中,所得之光固化產物之C2H5O+離子(m/z=45)對C3H7O+離子(m/z=59)的訊號強度比為5或更高且10或更低。但是,僅要求C2H5O+離子(m/z=45)的訊號強度應高於C3H7O+離子(m/z=59)的訊號強度。特定言之,此訊號強度比較佳地為1.1或更高,更佳地為2或更高。
已經以參考例示具體實施例的方式描述本發明,應瞭解本發明不限於所揭示的例示具體實施例。應以最寬廣範圍闡釋下列申請專利範圍的範圍,以含括所有的此修飾和對等結構及作用。
Claims (8)
- 一種藉由以光照射與模具接觸的光可固化組成物而得之光固化產物,該光固化產物含有含氟原子的界面活性劑,其中以飛行時間二次離子質譜術為基礎,藉光固化產物之表面分析而得的二次離子訊號中,C2H5O+離子訊號的強度高於C3H7O+離子訊號的強度。
- 如申請專利範圍第1項之光固化產物,其中該含氟原子的界面活性劑係包含環氧乙烷的化合物。
- 一種用以藉由與模具接觸並以光照射而得到光固化產物之光可固化組成物,該光可固化組成物具有至少一種可聚合的單體、光聚合引發劑、和含氟原子的界面活性劑,其中以飛行時間二次離子質譜術為基礎,藉光固化產物之表面分析而得的二次離子訊號中,C2H5O+離子訊號的強度高於C3H7O+離子訊號的強度。
- 一種用以在基板上形成具有預定圖案形狀的光固化產物之方法,包含:以光可固化組成物塗覆該基板;令該光可固化組成物與模具接觸;以光經由模具照射該光可固化組成物;和該光可固化組成物自模具脫模,其中該光固化產物係如申請專利範圍第1或2項之光固化產物。
- 一種製造電路基板之方法,包含: 將光可固化組成物施於基材上;令模具壓於光可固化組成物以在光可固化組成物中形成圖案;以光照射具有圖案的光可固化組成物而製造具有圖案的固化產物;和固化產物自模具脫模而在基材上形成以固化產物中的圖案為基礎之電路結構,其中該光固化產物係如申請專利範圍第1或2項之光固化產物。
- 一種製造具有上凸/下凹圖案的固化產物之方法,包含:將光可固化組成物施於基材上;令具有上凸/下凹表面的模具與光可固化組成物接觸而在光可固化組成物中形成對應的上凸/下凹圖案;以光照射該具有圖案的光可固化組成物而製造具有圖案的固化產物;和該固化產物自模具脫模而製得具有圖案的固化產物,其中該固化產物係如申請專利範圍第1或2項之光固化產物。
- 一種形成圖案之方法,包含:將光可固化組成物施於基材上;令具有上凸/下凹表面的模具與該光可固化組成物接觸而在該光可固化組成物中形成對應的上凸/下凹圖案;以光照射該具有圖案的光可固化組成物而製得具有圖 案的固化產物;和該固化產物自模具脫模而在該固化產物中形成圖案,其中該光固化產物係如申請專利範圍第1或2項之光固化產物。
- 如申請專利範圍第1或2項之光固化產物,其中該C2H5O+離子(m/z=45)對C3H7O+離子(m/z=59)的訊號強度比係2或更高。
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US10338467B2 (en) | 2013-09-18 | 2019-07-02 | Canon Kabushiki Kaisha | Method of producing film |
TWI643893B (zh) * | 2014-03-26 | 2018-12-11 | 日商富士軟片股份有限公司 | 光壓印用硬化性組成物、圖案形成方法及圖案 |
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TWI524382B (zh) | 2016-03-01 |
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JP2013165103A (ja) | 2013-08-22 |
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