TW201900735A - 具有羰基結構的含矽抗蝕下層膜形成組成物 - Google Patents
具有羰基結構的含矽抗蝕下層膜形成組成物 Download PDFInfo
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- UEUXEIHYBASMLX-UHFFFAOYSA-N trichloro-[phenyl(propan-2-yloxy)methyl]silane Chemical compound CC(C)OC([Si](Cl)(Cl)Cl)C1=CC=CC=C1 UEUXEIHYBASMLX-UHFFFAOYSA-N 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- UNKMHLWJZHLPPM-UHFFFAOYSA-N triethoxy(oxiran-2-ylmethoxymethyl)silane Chemical compound CCO[Si](OCC)(OCC)COCC1CO1 UNKMHLWJZHLPPM-UHFFFAOYSA-N 0.000 description 1
- OHKFEBYBHZXHMM-UHFFFAOYSA-N triethoxy-[1-(oxiran-2-ylmethoxy)butyl]silane Chemical compound CCO[Si](OCC)(OCC)C(CCC)OCC1CO1 OHKFEBYBHZXHMM-UHFFFAOYSA-N 0.000 description 1
- NFRRMEMOPXUROM-UHFFFAOYSA-N triethoxy-[1-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)C(CC)OCC1CO1 NFRRMEMOPXUROM-UHFFFAOYSA-N 0.000 description 1
- UDUKMRHNZZLJRB-UHFFFAOYSA-N triethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OCC)(OCC)OCC)CCC2OC21 UDUKMRHNZZLJRB-UHFFFAOYSA-N 0.000 description 1
- FVMMYGUCXRZVPJ-UHFFFAOYSA-N triethoxy-[2-(oxiran-2-ylmethoxy)butyl]silane Chemical compound CCO[Si](OCC)(OCC)CC(CC)OCC1CO1 FVMMYGUCXRZVPJ-UHFFFAOYSA-N 0.000 description 1
- RWJUTPORTOUFDY-UHFFFAOYSA-N triethoxy-[2-(oxiran-2-ylmethoxy)ethyl]silane Chemical compound CCO[Si](OCC)(OCC)CCOCC1CO1 RWJUTPORTOUFDY-UHFFFAOYSA-N 0.000 description 1
- CFUDQABJYSJIQY-UHFFFAOYSA-N triethoxy-[2-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CC(C)OCC1CO1 CFUDQABJYSJIQY-UHFFFAOYSA-N 0.000 description 1
- NLKPPXKQMJDBFO-UHFFFAOYSA-N triethoxy-[3-(7-oxabicyclo[4.1.0]heptan-4-yl)propyl]silane Chemical compound C1C(CCC[Si](OCC)(OCC)OCC)CCC2OC21 NLKPPXKQMJDBFO-UHFFFAOYSA-N 0.000 description 1
- KPNCYSTUWLXFOE-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)butyl]silane Chemical compound CCO[Si](OCC)(OCC)CCC(C)OCC1CO1 KPNCYSTUWLXFOE-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- PSUKBUSXHYKMLU-UHFFFAOYSA-N triethoxy-[4-(7-oxabicyclo[4.1.0]heptan-4-yl)butyl]silane Chemical compound C1C(CCCC[Si](OCC)(OCC)OCC)CCC2OC21 PSUKBUSXHYKMLU-UHFFFAOYSA-N 0.000 description 1
- GSUGNQKJVLXBHC-UHFFFAOYSA-N triethoxy-[4-(oxiran-2-ylmethoxy)butyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCCOCC1CO1 GSUGNQKJVLXBHC-UHFFFAOYSA-N 0.000 description 1
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 1
- JOHWNGGYGAVMGU-UHFFFAOYSA-N trifluorochlorine Chemical compound FCl(F)F JOHWNGGYGAVMGU-UHFFFAOYSA-N 0.000 description 1
- NLSFXUALGZKXNV-UHFFFAOYSA-N trimethoxy(3-propoxypropyl)silane Chemical compound CCCOCCC[Si](OC)(OC)OC NLSFXUALGZKXNV-UHFFFAOYSA-N 0.000 description 1
- LFBULLRGNLZJAF-UHFFFAOYSA-N trimethoxy(oxiran-2-ylmethoxymethyl)silane Chemical compound CO[Si](OC)(OC)COCC1CO1 LFBULLRGNLZJAF-UHFFFAOYSA-N 0.000 description 1
- FFJVMNHOSKMOSA-UHFFFAOYSA-N trimethoxy-[1-(oxiran-2-ylmethoxy)butyl]silane Chemical compound CCCC([Si](OC)(OC)OC)OCC1CO1 FFJVMNHOSKMOSA-UHFFFAOYSA-N 0.000 description 1
- FNBIAJGPJUOAPB-UHFFFAOYSA-N trimethoxy-[1-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)C(CC)OCC1CO1 FNBIAJGPJUOAPB-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- HTVULPNMIHOVRU-UHFFFAOYSA-N trimethoxy-[2-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CC(C)OCC1CO1 HTVULPNMIHOVRU-UHFFFAOYSA-N 0.000 description 1
- DBUFXGVMAMMWSD-UHFFFAOYSA-N trimethoxy-[3-(7-oxabicyclo[4.1.0]heptan-4-yl)propyl]silane Chemical compound C1C(CCC[Si](OC)(OC)OC)CCC2OC21 DBUFXGVMAMMWSD-UHFFFAOYSA-N 0.000 description 1
- ZQPNGHDNBNMPON-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)butyl]silane Chemical compound CO[Si](OC)(OC)CCC(C)OCC1CO1 ZQPNGHDNBNMPON-UHFFFAOYSA-N 0.000 description 1
- ZOWVSEMGATXETK-UHFFFAOYSA-N trimethoxy-[4-(7-oxabicyclo[4.1.0]heptan-4-yl)butyl]silane Chemical compound C1C(CCCC[Si](OC)(OC)OC)CCC2OC21 ZOWVSEMGATXETK-UHFFFAOYSA-N 0.000 description 1
- GUKYSRVOOIKHHB-UHFFFAOYSA-N trimethoxy-[4-(oxiran-2-ylmethoxy)butyl]silane Chemical compound CO[Si](OC)(OC)CCCCOCC1CO1 GUKYSRVOOIKHHB-UHFFFAOYSA-N 0.000 description 1
- PEIANZNHTIDHQE-UHFFFAOYSA-N trimethyl(3,3,3-trifluoropropyl)silane Chemical compound C[Si](C)(C)CCC(F)(F)F PEIANZNHTIDHQE-UHFFFAOYSA-N 0.000 description 1
- BKOOMYPCSUNDGP-UHFFFAOYSA-N trimethyl-ethylene Natural products CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 1
- 150000005199 trimethylbenzenes Chemical class 0.000 description 1
- YMCDISDNGWJEGJ-UHFFFAOYSA-N triphenyl(propoxy)silane Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(OCCC)C1=CC=CC=C1 YMCDISDNGWJEGJ-UHFFFAOYSA-N 0.000 description 1
- NBNZEBUNZGWIRJ-UHFFFAOYSA-N triphenylsulfanium;nitrate Chemical compound [O-][N+]([O-])=O.C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 NBNZEBUNZGWIRJ-UHFFFAOYSA-N 0.000 description 1
- ITHPEWAHFNDNIO-UHFFFAOYSA-N triphosphane Chemical compound PPP ITHPEWAHFNDNIO-UHFFFAOYSA-N 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- XMUJIPOFTAHSOK-UHFFFAOYSA-N undecan-2-ol Chemical compound CCCCCCCCCC(C)O XMUJIPOFTAHSOK-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000005050 vinyl trichlorosilane Substances 0.000 description 1
Classifications
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- 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
- G03F7/075—Silicon-containing compounds
- G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
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- H—ELECTRICITY
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- 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
- H01L21/0276—Photolithographic processes using an anti-reflective coating
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- 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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
- C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/16—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers in which all the silicon atoms are connected by linkages other than oxygen atoms
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- G—PHYSICS
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- 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
- G03F1/80—Etching
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- G—PHYSICS
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- 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
- G03F7/0042—Photosensitive materials with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists
- G03F7/0043—Chalcogenides; Silicon, germanium, arsenic or derivatives thereof; Metals, oxides or alloys thereof
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- 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
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
-
- 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
- G03F7/075—Silicon-containing compounds
- G03F7/0752—Silicon-containing compounds in non photosensitive layers or as additives, e.g. for dry lithography
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- 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
- G03F7/2014—Contact or film exposure of light sensitive plates such as lithographic plates or circuit boards, e.g. in a vacuum frame
- G03F7/2016—Contact mask being integral part of the photosensitive element and subject to destructive removal during post-exposure processing
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- 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
- H01L21/02041—Cleaning
- H01L21/02057—Cleaning during device manufacture
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- 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
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- 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
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- 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
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/26—Bombardment with radiation
- H01L21/263—Bombardment with radiation with high-energy radiation
- H01L21/265—Bombardment with radiation with high-energy radiation producing ion implantation
- H01L21/266—Bombardment with radiation with high-energy radiation producing ion implantation using masks
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- 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
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/308—Chemical or electrical treatment, e.g. electrolytic etching using masks
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
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- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- General Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
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- Toxicology (AREA)
- Materials For Photolithography (AREA)
- Silicon Polymers (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
Abstract
本發明係關於提供一種無需使光刻後的光罩殘渣進行蝕刻下,僅可藉由藥液除去之使用於形成抗蝕下層膜之組成物。 本發明係關於欲形成含矽抗蝕下層膜之組成物,該含矽抗蝕下層膜為,在以光刻加工使圖型轉印於下層後,對於以含有過氧化氫之藥液進行光罩層之除去的步驟中,作為該光罩層使用之膜,前述組成物係以含有具有單位結構之聚矽氧烷為特徴之含矽抗蝕下層膜形成組成物,該單位結構為具有含有羰基之官能基之單位結構。具有含有羰基之官能基之單位結構為含有環狀酸酐基、環狀二酯基,或二酯基之單位結構的上述記載之含矽抗蝕下層膜形成組成物。聚矽氧烷為進一步含有具有有機基的單位結構,該單位結構為具有含有醯胺基之有機基者。醯胺基為磺醯胺基,或二烯丙基異氰脲酸酯基。
Description
本發明係關於使用於半導體裝置的製造之欲於基板與抗蝕(例如光阻、電子線抗蝕)之間形成下層膜之組成物。詳細為有關於對於半導體裝置製造之光刻步驟,欲形成使用於光阻之下層的下層膜之光刻用抗蝕下層膜形成組成物。又,有關於使用該下層膜形成組成物之抗蝕圖型的形成方法。
對於自過去的半導體裝置之製造,已有藉由使用光阻之光刻的微細加工。前述微細加工為,於矽晶圓等半導體基板上形成光阻之薄膜,於其上介著描繪半導體裝置之圖型的光罩圖型照射紫外線等活性光線使其顯影,藉由將所得之光阻圖型作為保護膜而使基板進行蝕刻處理,於基板表面上,形成對應前述圖型之微細凹凸的加工法。然而,近年來,隨著半導體裝置之高度集成化的進行,所使用的活性光線亦有由KrF準分子雷射(248nm)至ArF準分子雷射(193nm)之短波長化的傾向。隨之自活性光線的半導體基板之反射的影響成為大問題。
又,作為半導體基板與光阻之間的下層膜,已有使用作為含有矽或鈦等金屬元素之硬光罩為已知的膜。此時,在抗蝕與硬光罩,因該構成成分有著很大的相異性,故藉由這些乾蝕刻的被除去之速度,取決於使用於乾蝕刻之氣體種類。而藉由適當地選擇氣體種類,不會造成光阻膜厚之大量減少,且硬光罩可藉由乾蝕刻而除去。如此對於近年的半導體裝置之製造,欲主要達成反射防止效及種種效果,於半導體基板與光阻之間逐漸有配置抗蝕下層膜。而至今雖已有討論有關抗蝕下層膜用之組成物,但由所要求的特性之多様性等,期待抗蝕下層膜用之新穎材料之開發。
例如,已有人提出使用具有酯鍵之矽烷的含有聚矽氧烷之抗蝕下層膜(參照專利文獻1、專利文獻2、專利文獻3)。 [先前技術文獻] [專利文獻]
[專利文獻1] 特開2007-226170號公報 [專利文獻2] 特開2004-310019號公報 [專利文獻3] 國際公開手冊WO2006/057782
[發明所解決的問題]
藉由半導體最先端裝置之植入層的微細化,多層製程已廣泛被使用。通常在多層製程中,對下層的轉印係藉由乾蝕刻而進行,最終基板的加工亦以乾蝕刻進行。又,基板之加工後的光罩殘渣,例如含有抗蝕或抗蝕下層膜的有機下層膜之除去亦於乾蝕刻或灰化處理中進行,但對基板會造成損傷,故要求改善。
本發明之目的為提供一種可使用於半導體裝置之製造上的光刻用抗蝕下層膜形成組成物。詳細為提供一種欲形成可作為硬光罩使用的抗蝕下層膜之光刻用抗蝕下層膜形成組成物。又,提供一種欲形成可作為反射防止膜使用的抗蝕下層膜之光刻用抗蝕下層膜形成組成物。又,提供一種與抗蝕不會互混,與抗蝕比較具有較大乾蝕刻速度之光刻用抗蝕下層膜及欲形成該下層膜的抗蝕下層膜形成組成物。 [解決課題的手段]
作為本發明之第1觀點的含矽抗蝕下層膜形成組成物,其為欲形成含矽抗蝕下層膜之組成物,其特徵為該含矽抗蝕下層膜為在以光刻加工將圖型轉印至下層後,以含有過氧化氫的藥液進行光罩層之除去的步驟中,作為該光罩層使用的膜,前述組成物為含有具有單位結構的聚矽氧烷,該單位結構為具有含有羰基之官能基者。 作為第2觀點的如第1觀點所記載的含矽抗蝕下層膜形成組成物,其中具有含有羰基之官能基的單位結構為,含有環狀酸酐基、環狀二酯基,或二酯基之單位結構。 作為第3觀點的如第1觀點所記載的含矽抗蝕下層膜形成組成物,其中上述聚矽氧烷為含有下述式(1)所示矽烷之水解性矽烷的水解縮合物。 式(1):[式(1)中,R1
表示含有式(1-1)、式(1-2)、式(1-3)、式(1-4)、式(1-5),或式(1-6):(式中,T1
、T4
表示伸烷基或環狀伸烷基,T2
表示烷基,T3
表示各環狀伸烷基。n表示1或2的整數。T11
、T15
,及T18
表示伸烷基、環狀伸烷基、伸烯基、伸芳基、硫原子、氧原子、氧羰基、醯胺基、2級胺基,或此等組合,T12
、T13
、T14
、T16
、T17
、T19
及T20
各表示氫原子或烷基,T21
表示伸烷基。※表示直接或經由連結基與矽原子之鍵結部位。)的有機基,且藉由Si-C鍵與矽原子鍵結者。 式(1)中,R2
表示烷基、芳基、鹵化烷基、鹵化芳基、烯基,或具有環氧基、丙烯醯基、甲基丙烯醯基、巰基、胺基,或者氰基的有機基,且藉由Si-C鍵與矽原子鍵結者。 式(1)中R3
表示烷氧基、醯氧基,或鹵素原子。a表示1的整數,b表示0或1的整數,a+b表示1或2的整數]。 作為第4觀點的如第1觀點或第2觀點所記載的含矽抗蝕下層膜形成組成物,其中上述聚矽氧烷為進一步含有有機基的單位結構,該有機基為含有醯胺基。 作為第5觀點的如第4觀點所記載的含矽抗蝕下層膜形成組成物,其中醯胺基為磺醯胺基,或二烯丙基異氰脲酸酯基。 作為第6觀點的如第1觀點所記載的含矽抗蝕下層膜形成組成物,其中上述聚矽氧烷為含有上述式(1)所示矽烷及下述式(2)所示矽烷之水解性矽烷的共水解縮合物。 式(2):[式(2)中,R4
表示含有式(2-1),或式(2-2):的有機基,且藉由Si-C鍵與矽原子鍵結者。 式(2)中,R5
表示烷基、芳基、鹵化烷基、鹵化芳基、烯基,或具有環氧基、丙烯醯基、甲基丙烯醯基、巰基、胺基,或者氰基的有機基,且藉由Si-C鍵與矽原子鍵結者。 式(2)中,R6
表示烷氧基、醯氧基,或鹵素原子。a表示1個整數,b表示0或1的整數,a+b表示1或2的整數。※表示直接或經由連結基與矽原子之鍵結部位]。 作為第7觀點的如第1觀點所記載的含矽抗蝕下層膜形成組成物,其中上述聚矽氧烷為含有上述式(1)所示矽烷、上述式(2)所示矽烷與其他矽烷之水解性矽烷的共水解縮合物,其他矽烷為選自由式(3)所示矽烷及式(4)所示矽烷所成群的至少1種矽烷,(式(3)中,R7
表示烷基、芳基、鹵化烷基、鹵化芳基、烯基,或具有環氧基、丙烯醯基、甲基丙烯醯基、巰基,或者氰基之有機基,且藉由Si-C鍵與矽原子鍵結者,R8
表示烷氧基、醯氧基,或鹵素原子,a表示0至3的整數)。(式(4)中,R9
表示烷基,且藉由Si-C鍵與矽原子鍵結者,R10
表示烷氧基、醯氧基,或鹵素基,Y表示伸烷基或伸芳基,b表示0或1的整數,c表示0或1的整數)。 作為第8觀點的如第1觀點至第7觀點中任一所記載的含矽抗蝕下層膜形成組成物,其中進一步含有光酸產生劑。 作為第9觀點的如第1觀點至第8觀點中任一所記載的含矽抗蝕下層膜形成組成物,其中進一步含有金屬氧化物。 作為第10觀點的如第1觀點至第9觀點中任一所記載的含矽抗蝕下層膜形成組成物,其中上述含有過氧化氫之藥液為含有氨與過氧化氫之水溶液、含有鹽酸與過氧化氫之水溶液、含有硫酸與過氧化氫之水溶液,或含有氫氟酸與過氧化氫之水溶液。 作為第11觀點的抗蝕下層膜之製造方法,其特徵為將如第1觀點至第10觀點中任一所記載的抗蝕下層膜形成組成物塗布於半導體基板上經燒成而得者。 作為第12觀點的半導體裝置之製造方法,其特徵為含有以下步驟者,將如第1觀點至第10觀點中任一所記載的抗蝕下層膜形成組成物塗布於半導體基板上,經燒成後形成抗蝕下層膜的步驟、於前述下層膜上面塗布抗蝕用組成物而形成抗蝕膜之步驟、使前述抗蝕膜進行曝光的步驟、於曝光後顯影抗蝕而得到抗蝕圖型之步驟、藉由抗蝕圖型使抗蝕下層膜進行蝕刻的步驟,及藉由經圖型化的抗蝕與抗蝕下層膜使半導體基板進行加工的步驟、將光罩層以含有過氧化氫之藥液進行除去的步驟。 作為第13觀點的半導體裝置之製造方法,其特徵為具有以下步驟者,於半導體基板上形成有機下層膜的步驟、於上面塗布如第1觀點至第10觀點中任一所記載的抗蝕下層膜形成組成物,經燒成後形成抗蝕下層膜之步驟、於前述抗蝕下層膜上面塗布抗蝕用組成物而形成抗蝕層之步驟、使前述抗蝕膜進行曝光的步驟、於曝光後使抗蝕顯影而得到抗蝕圖型之步驟、藉由抗蝕圖型使抗蝕下層膜進行蝕刻的步驟、藉由經圖型化的抗蝕下層膜使有機下層膜進行蝕刻之步驟,及藉由經圖型化的有機下層膜使半導體基板進行加工之步驟、將光罩層以含有過氧化氫之藥液除去的步驟。 作為第14觀點的如第12觀點或第13觀點所記載的半導體裝置之製造方法,其中上述基板的加工為蝕刻,或離子注入。 作為第15觀點的如第12觀點至第13觀點中任一所記載的半導體裝置之製造方法,其中光罩層為含有抗蝕或抗蝕下層膜之有機下層膜。 [發明之效果]
本案為,基板加工後的光罩殘渣,例如含有抗蝕或抗蝕下層膜的有機下層膜之除去可藉由藥液進行,即使為含矽抗蝕下層膜等矽系的光罩殘渣,亦可藉由藥液而容易除去的抗蝕下層膜,進而製造出基板損傷較少的半導體裝置。
上述藥液為含有過氧化氫之藥液,其為含有氨與過氧化氫之水溶液(SC-1藥液)、含有鹽酸與過氧化氫之水溶液(SC-2藥液)、含有硫酸與過氧化氫之水溶液(SPM藥液),或含有氫氟酸與過氧化氫之水溶液(FPM藥液),提供一種這些藥液之除去性優良之抗蝕下層膜形成組成物。
特別為本發明之抗蝕下層膜在蝕刻半導體基板,或藉由離子注入進行加工的步驟後,將含有作為光罩層之抗蝕或抗蝕下層膜的有機下層膜以含有過氧化氫的藥液除去之步驟上為有效。
[實施發明之形態]
本發明的含矽抗蝕下層膜形成組成物為,在以光刻加工將圖型轉印於下層後,以含有過氧化氫之藥液進行含於含矽抗蝕下層膜之光罩層的除去之步驟時,其中所使用的含矽抗蝕下層膜在形成時使用的組成物,該組成物為含有具有單位結構的聚矽氧烷,該單位結構為具有含有羰基之官能基者。
本發明之抗蝕下層膜形成組成物為含有式(1)的水解性矽烷之水解縮合物(聚合物)與溶劑。又,可使用水解性矽烷為式(1)的水解性矽烷與式(2)的水解性矽烷之組合,又式(1)的水解性矽烷與式(2)的水解性矽烷,及式(3)的水解性矽烷之組合,又式(1)的水解性矽烷與式(3)的水解性矽烷之組合,又式(1)的水解性矽烷、式(2)的水解性矽烷、式(3)的水解性矽烷、式(4)的水解性矽烷之組合所成的水解性矽烷之水解縮合物。
而作為任意成分,可含有酸、水、醇、硬化觸媒、酸產生劑、其他有機聚合物、吸光性化合物,及界面活性劑等。
本發明之抗蝕下層膜形成組成物中之固體成分,例如為0.1質量%至50質量%,或0.1質量%至30質量%、0.1質量%至25質量%。其中所謂固體成分表示由抗蝕下層膜形成組成物之全成分除去溶劑成分者。
固體成分中所佔的水解性矽烷、其水解物,及其水解縮合物之比例為20質量%以上,例如為50質量%至100質量%、60質量%至100質量%、70質量%至100質量%。 得到水解縮合物時,未完全水解的部分水解物或矽烷化合物會混合於水解縮合物,亦可使用該混合物。該縮合物為具有聚矽氧烷結構之聚合物。
使用於本發明的水解性矽烷可含有上述式(1)之矽烷。 式中,R1
表示含有上述式(1-1)、式(1-2)、式(1-3)、式(1-4)、式(1-5),或式(1-6)之有機基,且藉由Si-C鍵與矽原子鍵結者。
式(1-1)、式(1-2),及式(1-3)中,T1
、T4
表示伸烷基或環狀伸烷基,T2
表示烷基,T3
表示各環狀伸烷基。n表示1或2的整數),且藉由Si-C鍵與矽原子鍵結者。 式(1-4)、式(1-5)、式(1-6)中,T11
、T15
,及T18
表示伸烷基、環狀伸烷基、伸烯基、伸芳基、硫原子、氧原子、氧羰基、醯胺基、2級胺基,或此等組合,T12
、T13
、T14
、T16
、T17
、T19
及T20
各表示氫原子或烷基,T21
表示伸烷基。
R2
表示烷基、芳基、鹵化烷基、鹵化芳基、烯基,或具有環氧基、丙烯醯基、甲基丙烯醯基、巰基、胺基,或者氰基之有機基,且藉由Si-C鍵與矽原子鍵結者。R3
表示烷氧基、醯氧基,或鹵素基。a表示1的整數,b表示0或1的整數,a+b表示1或2的整數。※表示直接或經由連結基與矽原子之鍵結部位。
使用於本發明的水解性矽烷可係含有式(1)之矽烷與式(2)之矽烷的水解性矽烷。
式中,R4
表示含有上述式(2-1),或式(2-2)之有機基,且藉由Si-C鍵與矽原子鍵結者。
R5
表示烷基、芳基、鹵化烷基、鹵化芳基、烯基,或具有環氧基、丙烯醯基、甲基丙烯醯基、巰基、胺基,或者氰基之有機基,且藉由Si-C鍵與矽原子鍵結者。R6
表示烷氧基、醯氧基,或鹵素基。a表示1的整數,b表示0或1的整數,a+b表示1或2的整數。※表示經由直接或連結物與矽原子的鍵結部位。
使用於本發明的水解性矽烷為,含有式(1)的矽烷與式(2)的矽烷與其他矽烷之水解性矽烷,其他矽烷為選自由式(3)與式(4)所成群的至少1種矽烷。
在式(3)的矽烷,式中,R7
表示烷基、芳基、鹵化烷基、鹵化芳基、烯基,或具有環氧基、丙烯醯基、甲基丙烯醯基、巰基,或者氰基之有機基,且藉由Si-C鍵與矽原子鍵結者,R8
表示烷氧基、醯氧基,或鹵素原子,a表示0至3的整數。
在式(4)的矽烷,式中,R9
表示烷基且藉由Si-C鍵與矽原子鍵結者,R10
表示烷氧基、醯氧基,或鹵素基,Y表示伸烷基或伸芳基,b表示0或1的整數,c表示0或1的整數。
上述烷基為具有直鏈或分支鏈之碳原子數1至10的烷基,例如可舉出甲基、乙基、n-丙基、i-丙基、n-丁基、i-丁基、s-丁基、t-丁基、n-戊基、1-甲基-n-丁基、2-甲基-n-丁基、3-甲基-n-丁基、1,1-二甲基-n-丙基、1,2-二甲基-n-丙基、2,2-二甲基-n-丙基、1-乙基-n-丙基、n-己基、1-甲基-n-戊基、2-甲基-n-戊基、3-甲基-n-戊基、4-甲基-n-戊基、1,1-二甲基-n-丁基、1,2-二甲基-n-丁基、1,3-二甲基-n-丁基、2,2-二甲基-n-丁基、2,3-二甲基-n-丁基、3,3-二甲基-n-丁基、1-乙基-n-丁基、2-乙基-n-丁基、1,1,2-三甲基-n-丙基、1,2,2-三甲基-n-丙基、1-乙基-1-甲基-n-丙基及1-乙基-2-甲基-n-丙基等。
又,亦可使用環狀烷基,例如作為碳原子數1至10的環狀烷基,可舉出環丙基、環丁基、1-甲基-環丙基、2-甲基-環丙基、環戊基、1-甲基-環丁基、2-甲基-環丁基、3-甲基-環丁基、1,2-二甲基-環丙基、2,3-二甲基-環丙基、1-乙基-環丙基、2-乙基-環丙基、環己基、1-甲基-環戊基、2-甲基-環戊基、3-甲基-環戊基、1-乙基-環丁基、2-乙基-環丁基、3-乙基-環丁基、1,2-二甲基-環丁基、1,3-二甲基-環丁基、2,2-二甲基-環丁基、2,3-二甲基-環丁基、2,4-二甲基-環丁基、3,3-二甲基-環丁基、1-n-丙基-環丙基、2-n-丙基-環丙基、1-i-丙基-環丙基、2-i-丙基-環丙基、1,2,2-三甲基-環丙基、1,2,3-三甲基-環丙基、2,2,3-三甲基-環丙基、1-乙基-2-甲基-環丙基、2-乙基-1-甲基-環丙基、2-乙基-2-甲基-環丙基及2-乙基-3-甲基-環丙基等。
伸烷基可舉出來自上述烷基之伸烷基。例如若為甲基則可舉出伸甲基,若為乙基可舉出伸乙基,若為丙基可舉出伸丙基。
作為烯基為碳數2至10的烯基,可舉出乙烯基、1-丙烯基、2-丙烯基、1-甲基-1-乙烯基、1-丁烯基、2-丁烯基、3-丁烯基、2-甲基-1-丙烯基、2-甲基-2-丙烯基、1-乙基乙烯基、1-甲基-1-丙烯基、1-甲基-2-丙烯基、1-戊烯基、2-戊烯基、3-戊烯基、4-戊烯基、1-n-丙基乙烯基、1-甲基-1-丁烯基、1-甲基-2-丁烯基、1-甲基-3-丁烯基、2-乙基-2-丙烯基、2-甲基-1-丁烯基、2-甲基-2-丁烯基、2-甲基-3-丁烯基、3-甲基-1-丁烯基、3-甲基-2-丁烯基、3-甲基-3-丁烯基、1,1-二甲基-2-丙烯基、1-i-丙基乙烯基、1,2-二甲基-1-丙烯基、1,2-二甲基-2-丙烯基、1-環戊烯基、2-環戊烯基、3-環戊烯基、1-己烯基、2-己烯基、3-己烯基、4-己烯基、5-己烯基、1-甲基-1-戊烯基、1-甲基-2-戊烯基、1-甲基-3-戊烯基、1-甲基-4-戊烯基、1-n-丁基乙烯基、2-甲基-1-戊烯基、2-甲基-2-戊烯基、2-甲基-3-戊烯基、2-甲基-4-戊烯基、2-n-丙基-2-丙烯基、3-甲基-1-戊烯基、3-甲基-2-戊烯基、3-甲基-3-戊烯基、3-甲基-4-戊烯基、3-乙基-3-丁烯基、4-甲基-1-戊烯基、4-甲基-2-戊烯基、4-甲基-3-戊烯基、4-甲基-4-戊烯基、1,1-二甲基-2-丁烯基、1,1-二甲基-3-丁烯基、1,2-二甲基-1-丁烯基、1,2-二甲基-2-丁烯基、1,2-二甲基-3-丁烯基、1-甲基-2-乙基-2-丙烯基、1-s-丁基乙烯基、1,3-二甲基-1-丁烯基、1,3-二甲基-2-丁烯基、1,3-二甲基-3-丁烯基、1-i-丁基乙烯基、2,2-二甲基-3-丁烯基、2,3-二甲基-1-丁烯基、2,3-二甲基-2-丁烯基、2,3-二甲基-3-丁烯基、2-i-丙基-2-丙烯基、3,3-二甲基-1-丁烯基、1-乙基-1-丁烯基、1-乙基-2-丁烯基、1-乙基-3-丁烯基、1-n-丙基-1-丙烯基、1-n-丙基-2-丙烯基、2-乙基-1-丁烯基、2-乙基-2-丁烯基、2-乙基-3-丁烯基、1,1,2-三甲基-2-丙烯基、1-t-丁基乙烯基、1-甲基-1-乙基-2-丙烯基、1-乙基-2-甲基-1-丙烯基、1-乙基-2-甲基-2-丙烯基、1-i-丙基-1-丙烯基、1-i-丙基-2-丙烯基、1-甲基-2-環戊烯基、1-甲基-3-環戊烯基、2-甲基-1-環戊烯基、2-甲基-2-環戊烯基、2-甲基-3-環戊烯基、2-甲基-4-環戊烯基、2-甲基-5-環戊烯基、2-伸甲基-環戊基、3-甲基-1-環戊烯基、3-甲基-2-環戊烯基、3-甲基-3-環戊烯基、3-甲基-4-環戊烯基、3-甲基-5-環戊烯基、3-伸甲基-環戊基、1-環己烯基、2-環己烯基及3-環己烯基等。
作為伸烯基,可舉出來自上述烯基之伸烯基。
作為芳基,可舉出碳數6至20的芳基,例如可舉出苯基、o-甲基苯基、m-甲基苯基、p-甲基苯基、o-氯苯基、m-氯苯基、p-氯苯基、o-氟苯基、p-巰基苯基、o-甲氧基苯基、p-甲氧基苯基、p-胺基苯基、p-氰苯基、α-萘基、β-萘基、o-聯苯基、m-聯苯基、p-聯苯基、1-蒽基、2-蒽基、9-蒽基、1-菲基、2-菲基、3-菲基、4-菲基及9-菲基。
作為伸芳基可舉出來自上述芳基之伸芳基。 又,可舉出這些氟、氯、溴,或碘等鹵素原子所取代之有機基。
藉由使用硫原子可形成硫醚鍵。使用氧原子時可形成醚鍵。使用氧羰基時可形成酯鍵。使用醯胺基時可形成醯胺鍵。使用2級胺基時可形成胺基。這些官能基可與上述例示組合而形成各鍵結。
作為環氧基的有機基,可舉出環氧丙氧基甲基、環氧丙氧基乙基、環氧丙氧基丙基、環氧丙氧基丁基、環氧環己基等。
作為具有丙烯醯基之有機基,可舉出丙烯醯基甲基、丙烯醯基乙基、丙烯醯基丙基等。
作為具有甲基丙烯醯基的有機基,可舉出甲基丙烯醯基甲基、甲基丙烯醯基乙基、甲基丙烯醯基丙基等。
作為具有巰基之有機基,可舉出乙基巰基、丁基巰基、己基巰基、辛基巰基等。
作為具有氰基之有機基,可舉出氰基乙基、氰基丙基等。
作為上述碳數1至20的烷氧基,可舉出具有碳數1至20的直鏈、分支、環狀烷基部分之烷氧基,例如可舉出甲氧基、乙氧基、n-丙氧基、i-丙氧基、n-丁氧基、i-丁氧基、s-丁氧基、t-丁氧基、n-戊氧基、1-甲基-n-丁氧基、2-甲基-n-丁氧基、3-甲基-n-丁氧基、1,1-二甲基-n-丙氧基、1,2-二甲基-n-丙氧基、2,2-二甲基-n-丙氧基、1-乙基-n-丙氧基、n-己氧基、1-甲基-n-戊氧基、2-甲基-n-戊氧基、3-甲基-n-戊氧基、4-甲基-n-戊氧基、1,1-二甲基-n-丁氧基、1,2-二甲基-n-丁氧基、1,3-二甲基-n-丁氧基、2,2-二甲基-n-丁氧基、2,3-二甲基-n-丁氧基、3,3-二甲基-n-丁氧基、1-乙基-n-丁氧基、2-乙基-n-丁氧基、1,1,2-三甲基-n-丙氧基、1,2,2-三甲基-n-丙氧基、1-乙基-1-甲基-n-丙氧基及1-乙基-2-甲基-n-丙氧基等,又作為環狀烷氧基,可舉出環丙氧基、環丁氧基、1-甲基-環丙氧基、2-甲基-環丙氧基、環戊氧基、1-甲基-環丁氧基、2-甲基-環丁氧基、3-甲基-環丁氧基、1,2-二甲基-環丙氧基、2,3-二甲基-環丙氧基、1-乙基-環丙氧基、2-乙基-環丙氧基、環己氧基、1-甲基-環戊氧基、2-甲基-環戊氧基、3-甲基-環戊氧基、1-乙基-環丁氧基、2-乙基-環丁氧基、3-乙基-環丁氧基、1,2-二甲基-環丁氧基、1,3-二甲基-環丁氧基、2,2-二甲基-環丁氧基、2,3-二甲基-環丁氧基、2,4-二甲基-環丁氧基、3,3-二甲基-環丁氧基、1-n-丙基-環丙氧基、2-n-丙基-環丙氧基、1-i-丙基-環丙氧基、2-i-丙基-環丙氧基、1,2,2-三甲基-環丙氧基、1,2,3-三甲基-環丙氧基、2,2,3-三甲基-環丙氧基、1-乙基-2-甲基-環丙氧基、2-乙基-1-甲基-環丙氧基、2-乙基-2-甲基-環丙氧基及2-乙基-3-甲基-環丙氧基等。
上述碳數2至20的醯氧基,例如可舉出甲基羰基氧基、乙基羰基氧基、n-丙基羰基氧基、i-丙基羰基氧基、n-丁基羰基氧基、i-丁基羰基氧基、s-丁基羰基氧基、t-丁基羰基氧基、n-戊基羰基氧基、1-甲基-n-丁基羰基氧基、2-甲基-n-丁基羰基氧基、3-甲基-n-丁基羰基氧基、1,1-二甲基-n-丙基羰基氧基、1,2-二甲基-n-丙基羰基氧基、2,2-二甲基-n-丙基羰基氧基、1-乙基-n-丙基羰基氧基、n-己基羰基氧基、1-甲基-n-戊基羰基氧基、2-甲基-n-戊基羰基氧基、3-甲基-n-戊基羰基氧基、4-甲基-n-戊基羰基氧基、1,1-二甲基-n-丁基羰基氧基、1,2-二甲基-n-丁基羰基氧基、1,3-二甲基-n-丁基羰基氧基、2,2-二甲基-n-丁基羰基氧基、2,3-二甲基-n-丁基羰基氧基、3,3-二甲基-n-丁基羰基氧基、1-乙基-n-丁基羰基氧基、2-乙基-n-丁基羰基氧基、1,1,2-三甲基-n-丙基羰基氧基、1,2,2-三甲基-n-丙基羰基氧基、1-乙基-1-甲基-n-丙基羰基氧基、1-乙基-2-甲基-n-丙基羰基氧基、苯基羰基氧基,及甲苯磺醯基羰基氧基等。
作為上述鹵素原子,可舉出氟、氯、溴、碘等。
式(1)的水解性矽烷可例出以下者。
又,式(2)的水解性矽烷如以下所例示。
上述式中,T為烷基,可舉出上述烷基的例示,例如以甲基、乙基為佳。
式(3)所示含矽化合物,例如可舉出四甲氧基矽烷、四氯矽烷、四乙醯氧基矽烷、四乙氧基矽烷、四n-丙氧基矽烷、四異丙氧基矽烷、四n-丁氧基矽烷、四乙醯氧基矽烷、甲基三甲氧基矽烷、甲基三氯矽烷、甲基乙醯氧基矽烷、甲基三丙氧基矽烷、甲基三乙醯氧基矽烷、甲基三丁氧基矽烷、甲基三丙氧基矽烷、甲基三辛氧基矽烷、甲基三苯氧基矽烷、甲基三苯甲氧基矽烷、甲基三苯乙氧基矽烷、環氧丙氧基甲基三甲氧基矽烷、環氧丙氧基甲基三乙氧基矽烷、αー環氧丙氧基乙基三甲氧基矽烷、α-環氧丙氧基乙基三乙氧基矽烷、β-環氧丙氧基乙基三甲氧基矽烷、β-環氧丙氧基乙基三乙氧基矽烷、α-環氧丙氧基丙基三甲氧基矽烷、α-環氧丙氧基丙基三乙氧基矽烷、β-環氧丙氧基丙基三甲氧基矽烷、β-環氧丙氧基丙基三乙氧基矽烷、γ-環氧丙氧基丙基三甲氧基矽烷、γ-環氧丙氧基丙基三乙氧基矽烷、γ-環氧丙氧基丙基三丙氧基矽烷、γ-環氧丙氧基丙基三丁氧基矽烷、γ-環氧丙氧基丙基三苯氧基矽烷、α-環氧丙氧基丁基三甲氧基矽烷、α-環氧丙氧基丁基三乙氧基矽烷、β-環氧丙氧基丁基三乙氧基矽烷、γ-環氧丙氧基丁基三甲氧基矽烷、γ-環氧丙氧基丁基三乙氧基矽烷、δ-環氧丙氧基丁基三甲氧基矽烷、δ-環氧丙氧基丁基三乙氧基矽烷、(3,4-環氧環己基)甲基三甲氧基矽烷、(3,4-環氧環己基)甲基三乙氧基矽烷、β-(3,4-環氧環己基)乙基三甲氧基矽烷、β-(3,4-環氧環己基)乙基三乙氧基矽烷、β-(3,4-環氧環己基)乙基三丙氧基矽烷、β-(3,4-環氧環己基)乙基三丁氧基矽烷、β-(3,4-環氧環己基)乙基三苯氧基矽烷、γ-(3,4-環氧環己基)丙基三甲氧基矽烷、γ-(3,4-環氧環己基)丙基三乙氧基矽烷、δ-(3,4-環氧環己基)丁基三甲氧基矽烷、δ-(3,4-環氧環己基)丁基三乙氧基矽烷、環氧丙氧基甲基甲基二甲氧基矽烷、環氧丙氧基甲基甲基二乙氧基矽烷、α-環氧丙氧基乙基甲基二甲氧基矽烷、α-環氧丙氧基乙基甲基二乙氧基矽烷、β-環氧丙氧基乙基甲基二甲氧基矽烷、β-環氧丙氧基乙基乙基二甲氧基矽烷、α-環氧丙氧基丙基甲基二甲氧基矽烷、α-環氧丙氧基丙基甲基二乙氧基矽烷、β-環氧丙氧基丙基甲基二甲氧基矽烷、β-環氧丙氧基丙基乙基二甲氧基矽烷、γ-環氧丙氧基丙基甲基二甲氧基矽烷、γ-環氧丙氧基丙基甲基二乙氧基矽烷、γ-環氧丙氧基丙基甲基二丙氧基矽烷、γ-環氧丙氧基丙基甲基二丁氧基矽烷、γ-環氧丙氧基丙基甲基二苯氧基矽烷、γ-環氧丙氧基丙基乙基二甲氧基矽烷、γ-環氧丙氧基丙基乙基二乙氧基矽烷、γ-環氧丙氧基丙基乙烯基二甲氧基矽烷、γ-環氧丙氧基丙基乙烯基二乙氧基矽烷、乙基三甲氧基矽烷、乙基三乙氧基矽烷、乙烯基三甲氧基矽烷、乙烯基三氯矽烷、乙烯基乙醯氧基矽烷、乙烯基三乙氧基矽烷、乙烯基乙醯氧基矽烷、甲氧基苯基三甲氧基矽烷、甲氧基苯基三乙氧基矽烷、甲氧基苯基乙醯氧基矽烷、甲氧基苯基三氯矽烷、甲氧基苯甲基三甲氧基矽烷、甲氧基苯甲基三乙氧基矽烷、甲氧基苯甲基乙醯氧基矽烷、甲氧基苯甲基三氯矽烷、甲氧基苯乙基三甲氧基矽烷、甲氧基苯乙基三乙氧基矽烷、甲氧基苯乙基乙醯氧基矽烷、甲氧基苯乙基三氯矽烷、乙氧基苯基三甲氧基矽烷、乙氧基苯基三乙氧基矽烷、乙氧基苯基乙醯氧基矽烷、乙氧基苯基三氯矽烷、乙氧基苯甲基三甲氧基矽烷、乙氧基苯甲基三乙氧基矽烷、乙氧基苯甲基乙醯氧基矽烷、乙氧基苯甲基三氯矽烷、異丙氧基苯基三甲氧基矽烷、異丙氧基苯基三乙氧基矽烷、異丙氧基苯基乙醯氧基矽烷、異丙氧基苯基三氯矽烷、異丙氧基苯甲基三甲氧基矽烷、異丙氧基苯甲基三乙氧基矽烷、異丙氧基苯甲基乙醯氧基矽烷、異丙氧基苯甲基三氯矽烷、t-丁氧基苯基三甲氧基矽烷、t-丁氧基苯基三乙氧基矽烷、t-丁氧基苯基乙醯氧基矽烷、t-丁氧基苯基三氯矽烷、t-丁氧基苯甲基三甲氧基矽烷、t-丁氧基苯甲基三乙氧基矽烷、t-丁氧基苯甲基乙醯氧基矽烷、t-丁氧基二苯甲基三氯矽烷、甲氧基萘三甲氧基矽烷、甲氧基萘三乙氧基矽烷、甲氧基萘乙醯氧基矽烷、甲氧基萘三氯矽烷、乙氧基萘三甲氧基矽烷、乙氧基萘三乙氧基矽烷、乙氧基萘乙醯氧基矽烷、乙氧基萘三氯矽烷、γ-氯丙基三甲氧基矽烷、γ-氯丙基三乙氧基矽烷、γ-氯丙基乙醯氧基矽烷、3、3、3-三氟丙基三甲氧基矽烷、γ-甲基丙烯酸氧基丙基三甲氧基矽烷、γ-巰基丙基三甲氧基矽烷、γ-巰基丙基三乙氧基矽烷、β-氰基乙基三乙氧基矽烷、氯甲基三甲氧基矽烷、氯甲基三乙氧基矽烷、二甲基二甲氧基矽烷、苯基甲基二甲氧基矽烷、二甲基二乙氧基矽烷、苯基甲基二乙氧基矽烷、γ-氯丙基甲基二甲氧基矽烷、γ-氯丙基甲基二乙氧基矽烷、二甲基二乙醯氧基矽烷、γ-甲基丙烯酸氧基丙基甲基二甲氧基矽烷、γ-甲基丙烯酸氧基丙基甲基二乙氧基矽烷、γ-巰基丙基甲基二甲氧基矽烷、γ-巰基甲基二乙氧基矽烷、甲基乙烯基二甲氧基矽烷、甲基乙烯基二乙氧基矽烷等。
又,式(3)的R7
之芳基以取代芳基為佳,例如可舉出取代苯基,作為這些烷氧基苯基或醯氧基苯基或含有此的有機基可例示的矽烷如以下所舉出。
式(4)所示含矽化合物,例如可舉出伸甲基雙三甲氧基矽烷、伸甲基雙三氯矽烷、伸甲基雙乙醯氧基矽烷、伸乙基雙三乙氧基矽烷、伸乙基雙三氯矽烷、伸乙基雙乙醯氧基矽烷、伸丙基雙三乙氧基矽烷、伸丁基雙三甲氧基矽烷、伸苯基雙三甲氧基矽烷、伸苯基雙三乙氧基矽烷、伸苯基雙甲基二乙氧基矽烷、伸苯基雙甲基二甲氧基矽烷、亞萘基雙三甲氧基矽烷、雙三甲氧基二矽烷、雙三乙氧基二矽烷、雙乙基二乙氧基二矽烷、雙甲基二甲氧基二矽烷等。
使用於本發明的水解縮合物之具體例子,可例示出以下。
上述水解性矽烷的水解縮合物(聚有機矽氧烷)可得到重量平均分子量1000至1000000,或1000至100000之縮合物。這些分子量可藉由GPC分析而由聚苯乙烯換算得到之分子量。
GPC之測定條件,例如可使用GPC裝置(商品名HLC-8220GPC、Tosoh股份有限公司製)、GPC管柱(商品名ShodexKF803L、KF802、KF801、昭和電工製)、管柱溫度為40℃、溶離液(溶離溶劑)為四氫呋喃、流量(流速)為1.0ml/min、標準試料為聚苯乙烯(昭和電工股份有限公司製)下進行。
烷氧基矽基、醯氧基矽基,或鹵化矽基的水解中,水解性基的1莫耳單位,使用0.5莫耳至100莫耳,較佳為1莫耳至10莫耳之水。
又,水解性基的1莫耳單位中可使用0.001莫耳至10莫耳,較佳為0.001莫耳至1莫耳的水解觸媒。
進行水解與縮合時的反應溫度,一般為20℃至80℃。
水解步驟可完全水解,亦可部分水解者。即,於水解縮合物中可殘留水解物或單體。 水解後進行縮合時可使用觸媒。
作為水解觸媒,可舉出金屬螯合化合物、有機酸、無機酸、有機鹼、無機鹼。
作為水解觸媒之金屬螯合化合物,例如可舉出三乙氧基・單(乙醯丙酮酸酯)鈦等鈦螯合化合物、三乙氧基・單(乙醯丙酮酸酯)鋯等鋯螯合化合物、參(乙醯丙酮酸酯)鋁等鋁螯合化合物。
作為水解觸媒之有機酸,例如可舉出乙酸、丙酸、丁烷酸、戊烷酸、己烷酸、庚烷酸、辛酸、壬酸、癸烷酸、草酸、馬來酸、甲基丙二酸、己二酸、癸二酸、没食子酸、丁酸、優點酸、花生四烯酸、2-乙基己烷酸、油酸、硬脂酸、亞油酸、Linoleic acid、水楊酸、安息香酸、p-胺基安息香酸、p-甲苯磺酸、苯磺酸、單氯乙酸、二氯乙酸、三氯乙酸、三氟乙酸、甲酸、丙二酸、磺酸、鄰苯二甲酸、富馬酸、檸檬酸、酒石酸等。
作為水解觸媒之無機酸,例如可舉出鹽酸、硝酸、硫酸、氫氟酸、磷酸等。
作為水解觸媒的有機鹼,例如可舉出吡啶、吡咯、哌嗪、吡咯烷、哌啶、甲基吡啶、三甲基胺、三乙基胺、單乙醇胺、二乙醇胺、二甲基單乙醇胺、單甲基二乙醇胺、三乙醇胺、二氮雜雙環辛烷、二氮雜雙環壬烷、二氮雜雙環十一碳烯、四甲基銨氫氧化物等。作為無機鹼,例如可舉出氨、氫氧化鈉、氫氧化鉀、氫氧化鋇、氫氧化鈣等。這些觸媒中,以金屬螯合化合物、有機酸、無機酸為佳,這些可使用1種或者同時使用2種以上。
作為使用於水解的有機溶劑,例如可舉出n-戊烷、i-戊烷、n-己烷、i-己烷、n-庚烷、i-庚烷、2,2,4-三甲基戊烷、n-辛烷、i-辛烷、環己烷、甲基環己烷等脂肪族烴系溶劑;苯、甲苯、二甲苯、乙基苯、三甲基苯、甲基乙基苯、n-丙基苯、i-丙基苯、二乙基苯、i-丁基苯、三乙基苯、二-i-丙基苯、n-戊基萘、三甲基苯等芳香族烴系溶劑;甲醇、乙醇、n-丙醇、i-丙醇、n-丁醇、i-丁醇、sec-丁醇、t-丁醇、n-戊醇、i-戊醇、2-甲基丁醇、sec-戊醇、t-戊醇、3-甲氧基丁醇、n-己醇、2-甲基戊醇、sec-己醇、2-乙基丁醇、sec-庚醇、庚醇-3、n-辛醇、2-乙基己醇、sec-辛醇、n-壬基醇、2,6-二甲基庚醇-4、n-癸醇、sec-十一烷基醇、三甲基壬基醇、sec-四癸基醇、sec-十七烷基醇、酚、環己醇、甲基環己醇、3,3,5-三甲基環己醇、苯甲基醇、苯基甲基甲醇(Carbinol)、二丙酮醇、甲酚等單醇系溶劑;乙二醇、丙二醇、1,3-丁二醇、戊烷二醇-2,4、2-甲基戊烷二醇-2,4、己二醇-2,5、庚烷二醇-2,4、2-乙基己二醇-1,3、二乙二醇、二丙二醇、三乙二醇、三丙二醇、甘油等多元醇系溶劑;丙酮、甲基乙基酮、甲基-n-丙基酮、甲基-n-丁基酮、二乙基酮、甲基-i-丁基酮、甲基-n-戊基酮、乙基-n-丁基酮、甲基-n-己基酮、二-i-丁基酮、三甲基壬酮、環己酮、甲基環己酮、2,4-戊烷二酮、丙酮基丙酮、二丙酮醇、苯乙酮、葑酮(Fenchone)等酮系溶劑;乙基醚、i-丙基醚、n-丁基醚、n-己基醚、2-乙基己基醚、環氧乙烷、1,2-環氧丙烷、二呋喃、4-甲基二呋喃、二噁烷、二甲基二噁烷、乙二醇單甲基醚、乙二醇單乙基醚、乙二醇二乙基醚、乙二醇單-n-丁基醚、乙二醇單-n-己基醚、乙二醇單苯基醚、乙二醇單-2-乙基丁基醚、乙二醇二丁基醚、二乙二醇單甲基醚、二乙二醇單乙基醚、二乙二醇二乙基醚、二乙二醇單-n-丁基醚、二乙二醇二-n-丁基醚、二乙二醇單-n-己基醚、乙氧基三甘醇、四乙二醇二-n-丁基醚、丙二醇單甲基醚、丙二醇單乙基醚、丙二醇單丙基醚、丙二醇單丁基醚、丙二醇單甲基醚乙酸酯、二丙二醇單甲基醚、二丙二醇單乙基醚、二丙二醇單丙基醚、二丙二醇單丁基醚、三丙二醇單甲基醚、四氫呋喃、2-甲基四氫呋喃等醚系溶劑;二乙基碳酸酯、乙酸甲基、乙酸乙酯、γ-丁內酯、γ-戊內酯、乙酸n-丙基、乙酸i-丙基、乙酸n-丁基、乙酸i-丁基、乙酸sec-丁基、乙酸n-戊基、乙酸sec-戊基、乙酸3-甲氧基丁基、乙酸甲基戊基、乙酸2-乙基丁基、乙酸2-乙基己基、乙酸苯甲基、乙酸環己基、乙酸甲基環己基、乙酸n-壬基、乙醯乙酸甲基、乙醯乙酸乙酯、乙酸乙二醇單甲基醚、乙酸乙二醇單乙基醚、乙酸二乙二醇單甲基醚、乙酸二乙二醇單乙基醚、乙酸二乙二醇單-n-丁基醚、乙酸丙二醇單甲基醚、乙酸丙二醇單乙基醚、乙酸丙二醇單丙基醚、乙酸丙二醇單丁基醚、乙酸二丙二醇單甲基醚、乙酸二丙二醇單乙基醚、二乙酸甘醇、乙酸甲氧基三甘醇、丙酸乙酯、丙酸n-丁酯、丙酸i-戊酯、草酸二乙酯、草酸二-n-丁酯、乳酸甲酯、乳酸乙酯、乳酸n-丁酯、乳酸n-戊酯、丙二酸二乙酯、鄰苯二甲酸二甲酯、鄰苯二甲酸二乙酯等酯系溶劑;N-甲基甲醯胺、N,N-二甲基甲醯胺、N,N-二乙基甲醯胺、乙醯胺、N-甲基乙醯胺、N,N-二甲基乙醯胺、N-甲基丙醯胺、N-甲基吡咯啶酮等含氮系溶劑;硫化二甲基、硫化二乙基、噻吩、四氫噻吩、二甲基亞碸、環丁碸、1,3-丙烷磺內酯等含硫系溶劑等。這些溶劑可使用1種或組合2種以上後使用。
特別以丙酮、甲基乙基酮、甲基-n-丙基酮、甲基-n-丁基酮、二乙基酮、甲基-i-丁基酮、甲基-n-戊基酮、乙基-n-丁基酮、甲基-n-己基酮、二-i-丁基酮、三甲基壬酮、環己酮、甲基環己酮、2,4-戊烷二酮、丙酮基丙酮、二丙酮醇、苯乙酮、葑酮(Fenchone)等酮系溶劑由溶液之保存安定性的觀點來看為佳。
又,作為添加劑,可添加雙酚S,或雙酚S衍生物。雙酚S,或雙酚S衍生物對於聚有機矽氧烷100質量份而言為0.01質量份至20質量份,或0.01質量份至10質量份,或0.01質量份至5質量份。
較佳的雙酚S,或雙酚S衍生物例示於以下。
本發明之抗蝕下層膜形成組成物可含有硬化觸媒。硬化觸媒為含有由水解縮合物所成的聚有機矽氧烷之塗布膜經加熱使其發揮硬化作用時的硬化觸媒。
作為硬化觸媒,可使用銨鹽、膦類、鏻鹽、硫鎓鹽。
作為銨鹽,可舉出具有式(D-1):(但,m表示2至11,nd
表示2至3的整數,R2 1
表示烷基或芳基,Yd -
表示陰離子)所示結構之第4級銨鹽、具有式(D-2):(但,R22
、R23
、R24
及R25
表示烷基或芳基,N表示氮原子,Yd -
表示陰離子,且R22
、R23
、R24
,及R25
為各藉由C-N鍵與氮原子鍵結者)所示結構之第4級銨鹽、 具有式(D-3):(但,R26
及R27
表示烷基或芳基,Yd -
表示陰離子)的結構之第4級銨鹽、 具有式(D-4):(但,R28
表示烷基或芳基,Yd -
表示陰離子)的結構之第4級銨鹽、 具有式(D-5):(但,R29
及R30
表示烷基或芳基,Yd -
表示陰離子)的結構之第4級銨鹽、 具有式(D-6):(但,m表示2至11,n表示2至3的整數,H表示氫原子,Yd -
表示陰離子)的結構之第3級銨鹽。 又,作為鏻鹽,可舉出式(D-7):(但,R31
、R32
、R33
,及R34
表示烷基或芳基,P表示磷原子,Yd -
表示陰離子,且R31
、R32
、R33
,及R34
為各藉由C-P鍵與磷原子鍵結者)所示第4級鏻鹽。 又,作為硫鎓鹽,可舉出式(D-8):(但,R15
、R16
,及R17
表示烷基或芳基,S表示硫原子,Yd -
表示陰離子,且R15
、R16
,及R17
各為藉由C-S鍵與硫原子鍵結者)所示第3級硫鎓鹽。
上述式(D-1)所示化合物為由胺衍生的第4級銨鹽,m表示2至11,nd
表示2至3的整數。該第4級銨鹽之R21
表示碳原子數1至18,較佳為2至10的烷基或芳基,例如可舉出乙基、丙基、丁基等直鏈烷基,或苯甲基、環己基、環己基甲基、二環戊二烯基等。又,陰離子(Yd -
)可舉出氯化物離子(Cl-
)、溴化物離子(Br-
)、碘化物離子(I-
)等鹵化物離子,或羧酸根(-COO-
)、磺酸根(-SO3 -
)、醇酸根( -O-
)等酸基。
上述式(D-2)所示化合物為R22
R23
R24
R25
N+
Yd -
所示第4級銨鹽。該第4級銨鹽之R22
、R23
、R24
及R25
為碳原子數1至18的烷基或芳基,或藉由Si-C鍵與矽原子鍵結之矽烷化合物。陰離子(Yd -
)為可舉出氯化物離子(Cl-
)、溴化物離子(Br-
)、碘化物離子(I-
)等鹵化物離子,或羧酸根( -COO-
)、磺酸根(-SO3 -
)、醇酸根(-O-
)等酸基。該第4級銨鹽可由市售品獲得,例如可例示出四甲基銨乙酸酯、四丁基銨乙酸酯、氯化三乙基苯甲基銨、溴化三乙基苯甲基銨、氯化三辛基甲基銨、氯化三丁基苯甲基銨、氯化三甲基苯甲基銨等。
上述式(D-3)所示化合物係由1-取代咪唑所衍生的第4級銨鹽,R26
及R27
為碳數1至18的烷基或芳基,R26
及R27
為具有碳數總和為7以上者為佳。例如,R26
可例示出甲基、乙基、丙基、苯基、苯甲基,R27
可例示出苯甲基、辛基、十八烷基。陰離子(Yd -
)可舉出氯化物離子(Cl-
)、溴化物離子(Br-
)、碘化物離子(I-
)等鹵化物離子,或羧酸根(-COO-
)、磺酸根(-SO3 -
)、醇酸根(-O-
)等酸基。該化合物可由市售品獲得,例如可將1-甲基咪唑、1-苯甲基咪唑等咪唑系化合物與溴化苯甲基、溴化甲基等鹵化烷基或鹵化芳基進行反應而製造。
上述式(D-4)所示化合物為由吡啶衍生的第4級銨鹽,R28
為碳原子數1至18,較佳為碳原子數4至18的烷基或芳基,例如可例示出丁基、辛基、苯甲基、月桂基。陰離子(Yd -
)可舉出氯化物離子(Cl-
)、溴化物離子(Br-
)、碘化物離子(I-
)等鹵化物離子或羧酸根(-COO-
)、磺酸根(-SO3 -
)、醇酸根(-O-
)等酸基。該化合物可由市售品獲得,例如可將吡啶與氯化月桂基、氯化苯甲基、溴化苯甲基、溴化甲基、溴化辛基等鹵化烷基,或鹵化芳基進行反應而製造。該化合物,例如可例示出氯化N-月桂基吡啶鎓、溴化N-苯甲基吡啶鎓等。
上述式(D-5)所示化合物為以甲基吡啶等作為代表的由取代吡啶衍生出的第4級銨鹽,R29
表示碳原子數1至18,較佳為4至18的烷基或芳基,例如可例示出甲基、辛基、月桂基、苯甲基等。R30
表示碳原子數1至18的烷基或芳基,例如由甲基吡啶所衍生的第4級銨時,R30
為甲基。陰離子(Yd -
)可舉出氯化物離子(Cl-
)、溴化物離子(Br-
)、碘化物離子(I-
)等鹵化物離子,或羧酸根(-COO-
)、磺酸根(-SO3 -
)、醇酸根(-O-
)等酸基。該化合物可由市售品獲得,例如可將甲基吡啶等取代吡啶,與溴化甲基、溴化辛基、氯化月桂基、氯化苯甲基、溴化苯甲基等鹵化烷基,或鹵化芳基進行反應而製造。該化合物,例如可例示出N-苯甲基甲基吡啶鎓氯化物、N-苯甲基甲基吡啶鎓溴化物、N-月桂基甲基吡啶鎓氯化物等。
上述式(D-6)所示化合物為由胺所衍生的第3級銨鹽,m表示2至11,nd
表示2至3的整數。又,陰離子(Yd -
)可舉出氯化物離子(Cl-
)、溴化物離子(Br-
)、碘化物離子(I-
)等鹵化物離子,或羧酸根(-COO-
)、磺酸根(-SO3 -
)、醇酸根(-O-
)等酸基。可藉由胺與羧酸或與酚等弱酸的反應而製造。作為羧酸,可舉出甲酸或乙酸,使用甲酸時,陰離子(Yd -
)為(HCOO-
),使用乙酸時,陰離子(Yd -
)為(CH3
COO-
)。又,使用酚時,陰離子(Yd -
)為(C6
H5
O-
)。
上述式(D-7)所示化合物為,具有R31
R32
R33
R34
P+
Yd -
之結構的第4級鏻鹽。R31
、R32
、R33
,及R34
為碳原子數1至18的烷基或芳基,或藉由Si-C鍵與矽原子鍵結之矽烷化合物,較佳為R31
至R34
的4個取代基中,3個為苯基或被取代之苯基,例如可例示出苯基或甲苯基,又剩下1個為碳原子數1至18的烷基、芳基,或藉由Si-C鍵與矽原子鍵結的矽烷化合物。又,陰離子(Yd -
)可舉出氯化物離子(Cl-
)、溴化物離子(Br-
)、碘化物離子(I-
)等鹵化物離子,或羧酸根(-COO-
)、磺酸根(-SO3 -
)、醇酸根( -O-
)等酸基。該化合物可作為市售品而獲得者,例如可舉出鹵化四n-丁基鏻、鹵化四n-丙基鏻等鹵化四烷基鏻、鹵化三乙基苯甲基鏻等鹵化三烷基苯甲基鏻、鹵化三苯基甲基鏻、鹵化三苯基乙基鏻等鹵化三苯基單烷基鏻、鹵化三苯基苯甲基鏻、鹵化四苯基鏻、鹵化三甲苯單芳基鏻,或鹵化三甲苯單烷基鏻(鹵素原子為氯原子或溴原子)。特別以鹵化三苯基甲基鏻、鹵化三苯基乙基鏻等鹵化三苯基單烷基鏻、鹵化三苯基苯甲基鏻等鹵化三苯基單芳基鏻、鹵化三甲苯單苯基鏻等鹵化三甲苯單芳基鏻或鹵化三甲苯單甲基鏻等鹵化三甲苯單烷基鏻(鹵素原子為氯原子或溴原子)為佳。
又,作為膦類,可舉出甲基膦、乙基膦、丙基膦、異丙基膦、異丁基膦、苯基膦等第一膦、二甲基膦、二乙基膦、二異丙基膦、二異戊基膦、二苯基膦等第二膦、三甲基膦、三乙基膦、三苯基膦、甲基二苯基膦、二甲基苯基膦等第三膦。
上述式(D-8)所示化合物為具有R15
R16
R17
S+
Yd -
的結構之第3級硫鎓鹽。R15
、R16
,及R17
為碳原子數1至18的烷基或芳基,或藉由Si-C鍵與矽原子鍵結的矽烷化合物,較佳為R15
至R17
的4個取代基中,3個為苯基或被取代之苯基,例如可例示出苯基或甲苯基,又剩下1個為碳原子數1至18的烷基,或芳基。又,陰離子(Yd -
)可舉出氯化物離子(Cl-
)、溴化物離子(Br-
)、碘化物離子(I-
)等鹵素離,或羧酸根(-COO-
)、磺酸根(-SO3 -
)、醇酸根(-O-
)等酸基。該化合物可作為市售品方式而獲得,例如可舉出鹵化三n-丁基硫鎓、鹵化三n-丙基硫鎓等鹵化四烷基硫鎓、鹵化二乙基苯甲基硫鎓等鹵化三烷基苯甲基硫鎓、鹵化二苯基甲基硫鎓、鹵化二苯基乙基硫鎓等鹵化二苯基單烷基硫鎓、鹵化三苯基硫鎓、(鹵素原子為氯原子或溴原子)、三n-丁基硫鎓羧酸根、三-丙基硫鎓羧酸根等四烷基鏻羧酸根、二乙基苯甲基硫鎓羧酸根等三烷基苯甲基硫鎓羧酸根、二苯基甲基硫鎓羧酸根、二苯基乙基硫鎓羧酸根等二苯基單烷基硫鎓羧酸根、三苯基硫鎓羧酸根。特別以使用鹵化三苯基硫鎓、三苯基硫鎓羧酸根為佳。
硬化觸媒對於聚有機矽氧烷100質量份而言為0.01質量份至10質量份,或0.01質量份至5質量份,或0.01質量份至3質量份。
將水解性矽烷在溶劑中使用觸媒而水解並縮合,所得之水解縮合物(聚合物)可藉由減壓蒸餾等同時除去副產物的醇或所使用的水解觸媒或水。又,使用於水解的酸或鹽基觸媒可由中和或離子交換而除去。而在本發明之光刻用抗蝕下層膜形成組成物中,含有該水解縮合物之抗蝕下層膜形成組成物因安定化故可添加有機酸、水、醇,或此等組合。
作為上述有機酸,例如可舉出草酸、丙二酸、甲基丙二酸、琥珀酸、馬來酸、蘋果酸、酒石酸、鄰苯二甲酸、檸檬酸、戊二酸、檸檬酸、乳酸、水楊酸等。其中亦以草酸、馬來酸等為佳。另外有機酸對於縮合物(聚有機矽氧烷)100質量份而言為0.1質量份至5.0質量份。又,另為水可使用純水、超純水、離子交換水等,該添加量對於抗蝕下層膜形成組成物100質量份而言為1質量份至20質量份。
又作為醇,以塗布後藉由加熱可飛散者為佳,例如可舉出甲醇、乙醇、丙醇、異丙醇、丁醇等。另外,醇對於抗蝕下層膜形成組成物100質量份而言為1質量份至20質量份。
本發明之光刻用下層膜形成組成物除上述成分以外,視必要可含有有機聚合物化合物、光酸產生劑及界面活性劑等。
藉由使用有機聚合物化合物,可調整由本發明之光刻用下層膜形成組成物所形成的抗蝕下層膜之乾蝕刻速度(每單位時間之膜厚減少量)、減衰係數及折射率等。
作為有機聚合物之化合物,並無特別限制,可使用種種有機聚合物。可使用縮聚合之聚合物及加成聚合之聚合物等。可用使用聚酯、聚苯乙烯、聚醯亞胺、丙烯酸聚合物、甲基丙烯酸聚合物、聚乙烯醚、酚酚醛清漆、萘酚酚醛清漆、聚醚、聚醯胺、聚碳酸酯等加成聚合之聚合物及縮聚合之聚合物。使用作為吸光部位發揮功能之苯環、萘環、蒽環、三嗪環、喹啉環,及喹喔啉環等具有芳香環結構之有機聚合物為佳。
作為如此有機聚合物化合物,例如可舉出將苯甲基丙烯酸酯、苯甲基甲基丙烯酸酯、苯基丙烯酸酯、萘丙烯酸酯、蒽基甲基丙烯酸酯、蒽基甲基甲基丙烯酸酯、苯乙烯、羥基苯乙烯、苯甲基乙烯基醚及N-苯基馬來醯亞胺等加成聚合性單體作為該結構單位而含有的加成聚合之聚合物,或酚酚醛清漆及萘酚酚醛清漆等縮聚合之聚合物。
作為有機聚合物化合物,使用加成聚合之聚合物時,該聚合物化合物可為均聚物,亦可為共聚物。加成聚合之聚合物的製造中可使用加成聚合性單體。作為如此加成聚合性單體,可舉出丙烯酸、丙烯酸甲酯、丙烯酸酯化合物、甲基丙烯酸酯化合物、丙烯醯胺化合物、甲基丙烯醯胺化合物、乙烯基化合物、苯乙烯化合物、馬來醯亞胺化合物、馬來酸酐、丙烯腈等。
作為聚合物使用縮聚合聚合物時,作為如此聚合物,例如可舉出甘醇化合物與二羧酸化合物之縮聚合的聚合物。作為甘醇化合物,可舉出二乙二醇、六甲二醇、丁二醇等。作為二羧酸化合物,可舉出琥珀酸、己二酸、對苯二甲酸、馬來酸酐等。又,例如可舉出聚均苯四甲醯亞胺、聚(p-伸苯基對苯二甲醯胺)、聚丁烯對苯二甲酸乙二醇酯、聚乙烯對苯二甲酸乙二醇酯等聚酯、聚醯胺、聚醯亞胺。
於有機聚合物化合物中含有羥基時,該羥基可與聚有機矽氧烷形成交聯反應。
作為有機聚合物化合物,其重量平均分子量,例如可使用1000至1000000,或3000至300000,或5000至200000,或10000至100000之聚合物化合物。
可使用僅一種有機聚合物化合物,或亦可組合二種以上使用。
使用有機聚合物化合物時,作為該比例,對於縮合物(聚有機矽氧烷)100質量份而言為1至200質量份,或5至100質量份,或10至50質量份,或20至30質量份。
本發明之抗蝕下層膜形成組成物中可含有酸產生劑。 作為酸產生劑,可舉出熱酸產生劑或光酸產生劑。 光酸產生劑在抗蝕的曝光時會產生酸。因此,可調整下層膜之酸度。此為欲將下層膜的酸度與上層的抗蝕之酸度一樣的一方法。又,藉由下層膜之酸度的調整,可調整於上層所形成的抗蝕之圖型形狀。
作為於本發明之抗蝕下層膜形成組成物所含的光酸產生劑,可舉出鎓鹽化合物、磺醯亞胺化合物,及二磺醯基二偶氮甲烷化合物等。
作為鎓鹽化合物,可舉出二苯基碘鎓六氟磷酸鹽、二苯基碘鎓三氟甲烷磺酸鹽、二苯基碘鎓九氟正丁烷磺酸鹽、二苯基碘鎓全氟正辛烷磺酸鹽、二苯基碘鎓樟腦磺酸鹽、雙(4-第三丁基苯基)碘鎓樟腦磺酸鹽及雙(4-第三丁基苯基)碘鎓三氟甲烷磺酸鹽等碘鎓鹽化合物,及三苯基硫鎓六氟銻酸鹽、三苯基硫鎓九氟正丁烷磺酸鹽、三苯基硫鎓樟腦磺酸鹽及三苯基硫鎓三氟甲烷磺酸鹽等硫鎓鹽化合物等。
作為磺醯亞胺化合物,例如可舉出N-(三氟甲烷磺醯氧基)琥珀酸醯亞胺、N-(九氟正丁烷磺醯氧基)琥珀酸醯亞胺、N-(樟腦磺醯氧基)琥珀酸醯亞胺及N-(三氟甲烷磺醯氧基)萘醯亞胺等。
作為二磺醯基二偶氮甲烷化合物,例如可舉出雙(三氟甲基磺醯基)二偶氮甲烷、雙(環己基磺醯基)二偶氮甲烷、雙(苯基磺醯基)二偶氮甲烷、雙(p-甲苯磺醯基)二偶氮甲烷、雙(2,4-二甲基苯磺醯基)二偶氮甲烷,及甲基磺醯基-p-甲苯磺醯基二偶氮甲烷等。
光酸產生劑可以僅使用一種,或組合二種以上使用。
使用光酸產生劑時,作為該比例,對於縮合物(聚有機矽氧烷)100質量份而言為0.01質量份至5質量份,或0.1質量份至3質量份,或0.5質量份至1質量份。
界面活性劑為,將本發明之光刻用抗蝕下層膜形成組成物塗布於基板時,在抑制針孔及變形等產生上有效。
作為於本發明之抗蝕下層膜形成組成物所含的界面活性劑,例如可舉出聚氧乙烯月桂基醚、聚氧乙烯硬脂基醚、聚氧乙烯十六烷基醚、聚氧乙烯油基醚等聚氧乙烯烷基醚類、聚氧乙烯辛基酚醚、聚氧乙烯壬基酚醚等聚氧乙烯烷基烯丙基醚類、聚氧乙烯・聚氧丙烯嵌段共聚物類、山梨糖醇單月桂酸酯、山梨糖醇單棕櫚酸酯、山梨糖醇單硬脂酸酯、山梨糖醇單油酸酯、山梨糖醇三油酸酯、山梨糖醇三硬脂酸酯等山梨糖醇脂肪酸酯類、聚氧乙烯山梨糖醇單月桂酸酯、聚氧乙烯山梨糖醇單棕櫚酸酯、聚氧乙烯山梨糖醇單硬脂酸酯、聚氧乙烯山梨糖醇三油酸酯、聚氧乙烯山梨糖醇三硬脂酸酯等聚氧乙烯山梨糖醇脂肪酸酯類等非離子系界面活性劑、商品名EFTOPEF301、EF303、EF352((股)Tochem Products製)、商品名MegafacF171、F173、R-08、R-30(大日本油墨化學工業(股)製)、FLUORADFC430、FC431(住友3M(股)製)、商品名Asahi GuardAG710,SurflonS-382、SC101、SC102、SC103、SC104、SC105、SC106(旭硝子(股)製)等氟系界面活性劑,及有機矽氧烷聚合物KP341(信越化學工業(股)製)等。這些界面活性劑可單獨使用,又亦可組合二種以上使用。使用界面活性劑時,作為該比例,對於、縮合物(聚有機矽氧烷)100質量份而言為0.0001至5質量份,或0.001至1質量份,或0.01至0.5質量份。
又,於本發明之抗蝕下層膜形成組成物中,可添加流變調整劑及接著補助劑等。流變調整劑在提高下層膜形成組成物之流動性上為有效。接著補助劑在提高半導體基板或抗蝕與下層膜之密著性上為有效。
作為使用於本發明之抗蝕下層膜形成組成物的溶劑,若可溶解前述固體成分之溶劑即可,並無特別限制下可使用。作為如此溶劑,例如可舉出甲基溶纖劑乙酸酯、乙基溶纖劑乙酸酯、丙二醇、丙二醇單甲基醚、丙二醇單乙基醚、甲基異丁基甲醇(Carbinol)、丙二醇單丁基醚、丙二醇單甲基醚乙酸酯、丙二醇單乙基醚乙酸酯、丙二醇單丙基醚乙酸酯、丙二醇單丁基醚乙酸酯、甲苯、二甲苯、甲基乙基酮、環戊酮、環己酮、2-羥基丙酸乙基、2-羥基-2-甲基丙酸乙酯、乙氧基乙酸乙酯、羥基乙酸乙酯、2-羥基-3-甲基丁烷酸甲酯、3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸乙酯、3-乙氧基丙酸甲酯、丙酮酸甲酯、丙酮酸乙酯、乙二醇單甲基醚、乙二醇單乙基醚、乙二醇單丙基醚、乙二醇單丁基醚、乙二醇單甲基醚乙酸酯、乙二醇單乙基醚乙酸酯、乙二醇單丙基醚乙酸酯、乙二醇單丁基醚乙酸酯、二乙二醇二甲基醚、二乙二醇二乙基醚、二乙二醇二丙基醚、二乙二醇二丁基醚丙二醇單甲基醚、丙二醇二甲基醚、丙二醇二乙基醚、丙二醇二丙基醚、丙二醇二丁基醚、乳酸乙酯、乳酸丙酯、乳酸異丙酯、乳酸丁酯、乳酸異丁酯、甲酸甲酯、甲酸乙酯、甲酸丙酯、甲酸異丙酯、甲酸丁酯、甲酸異丁酯、甲酸戊酯、甲酸異戊酯、乙酸甲酯、乙酸乙酯、乙酸戊酯、乙酸異戊酯、乙酸己酯、丙酸甲酯、丙酸乙酯、丙酸丙酯、丙酸異丙酯、丙酸丁酯、丙酸異丁酯、丁酸甲酯、丁酸乙酯、丁酸丙酯、丁酸異丙酯、丁酸丁酯、丁酸異丁酯、羥基乙酸乙酯、2-羥基-2-甲基丙酸乙酯、3-甲氧基-2-甲基丙酸甲酯、2-羥基-3-甲基丁酸甲酯、甲氧基乙酸乙酯、乙氧基乙酸乙酯、3-甲氧基丙酸甲酯、3-乙氧基丙酸乙酯、3-甲氧基丙酸乙酯、3-甲氧基丁基乙酸酯、3-甲氧基丙基乙酸酯、3-甲基-3-甲氧基丁基乙酸酯、3-甲基-3-甲氧基丁基丙酸酯、3-甲基-3-甲氧基丁基丁酸酯、乙醯乙酸甲酯、甲苯、二甲苯、甲基乙基酮、甲基丙基酮、甲基丁基酮、2-庚酮、3-庚酮、4-庚酮、環己酮、N、N-二甲基甲醯胺、N-甲基乙醯胺、N,N-二甲基乙醯胺、N-甲基吡咯啶酮、4-甲基-2-戊醇,及γ-丁內酯等。這些溶劑可單獨或組合二種以上後使用。
以下對於本發明之抗蝕下層膜形成組成物之使用做說明。
使用於半導體裝置的製造之基板(例如矽晶圓基板、矽/二氧化矽被覆基板、氮化矽基板、玻璃基板、ITO基板、聚醯亞胺基板,及低介電率材料(low-k材料)被覆基板等)上面,藉由旋塗器、塗布器等適當塗布方法,塗布本發明之抗蝕下層膜形成組成物後,藉由燒成可形成抗蝕下層膜。作為燒成條件,可適宜地選自燒成溫度80℃至250℃、燒成時間0.3分鐘至60分鐘中者。較佳為燒成溫度150℃至250℃,燒成時間0.5分鐘至2分鐘。於此作為所形成的下層膜之膜厚,例如為10nm至1000nm,或20nm至500nm,或50nm至300nm,或100nm至200nm。
其次,於該抗蝕下層膜上面,例如形成光阻層。光阻層的形成可藉由公知方法,即可藉由光阻組成物溶液之下層膜上的塗布及燒成而進行。作為光阻之膜厚,例如為50nm至10000nm,或100nm至2000nm,或200nm至1000nm。
在本發明中,於基板上形成有機下層膜後,於該上面由本發明之組成物形成抗蝕下層膜,進一步可在該上面包覆光阻。藉此,光阻的圖型寬度會變窄,即使欲防止圖型倒下而使光阻薄薄地包覆時,亦可藉由選擇適當的蝕刻氣體而可對基板進行加工。例如,對於光阻,蝕刻速度變的非常快的氟系氣體作為蝕刻氣體時,可對於本發明之抗蝕下層膜進行加工,又對於本發明之抗蝕下層膜,蝕刻速度變的非常快的氧系氣體作為蝕刻氣體時,可進行有機下層膜之加工,進一步對於有機下層膜,蝕刻變的非常快的氟系氣體作為蝕刻氣體時,可進行基板之加工。
作為本發明之抗蝕下層膜的上面所形成的光阻,若可對使用於曝光的光具有感光者即可,並無特別限定。可使用負型光阻及正型光阻中任一種。有著由酚醛清漆樹脂與1,2-萘醌二疊氮化物磺酸酯所成的正型光阻、由具有藉由酸而分解使提高鹼溶解速度的基之黏合劑與光酸產生劑所成的化學增幅型光阻、由藉由酸而分解使光阻的鹼溶解速度提高的低分子化合物與鹼可溶性黏合劑與光酸產生劑所成的化學增幅型光阻,及由具有藉由酸而分解使鹼溶解速度提高的基之黏合劑與藉由酸而分解使光阻的鹼溶解速度提高的低分子化合物與光酸產生劑所成的化學增幅型光阻等。例如,可舉出希普利公司製商品名APEX-E、住友化學工業(股)製商品名PAR710,及信越化學工業(股)製商品名SEPR430等。又,例如可舉出Proc. SPIE, Vol. 3999, 330-334 (2000)、Proc. SPIE, Vol. 3999, 357-364 (2000)或Proc. SPIE, Vol. 3999, 365-374 (2000)所記載之含氟原子聚合物系光阻。
其次,通過所定光罩而進行曝光。曝光中,可使用KrF準分子雷射(波長248nm)、ArF準分子雷射(波長193nm)及F2準分子雷射(波長157nm)等。曝光後,視必要亦可進行曝光後加熱(post exposure bake)。曝光後加熱為適宜地選自加熱溫度70℃至150℃,加熱時間0.3分鐘至10分鐘的條件下進行。
又,在本發明中作為抗蝕可改善光阻而使用電子線光刻用抗蝕,或EUV光刻用抗蝕。作為電子線抗蝕,可使用負型、正型中任一種。有著由酸產生劑與具有使藉由酸進行分解的鹼溶解速度產生變化的基之黏合劑所成的化學增幅型抗蝕、由鹼可溶性黏合劑與酸產生劑與藉由酸進行分解使抗蝕的鹼溶解速度產生變化之低分子化合物所成的化學增幅型抗蝕、由酸產生劑與具有藉由酸進行分解而使鹼溶解速度產生變化的基之黏合劑與藉由酸進行分解而使抗蝕的鹼溶解速度產生變化的低分子化合物所成的化學增幅型抗蝕、由具有作為電子線進行分解而使鹼溶解速度產生變化的基之黏合劑所成的非化學增幅型抗蝕、由具有藉由電子線經切斷而使鹼溶解速度產生變化的部位之黏合劑所成的非化學增幅型抗蝕等。使用這些電子線抗蝕時,與將照射源作為電子線而使用光阻之情況同様地可形成抗蝕圖型。
又,作為EUV抗蝕可使用甲基丙烯酸酯樹脂系抗蝕。
其次,藉由顯影液(例如鹼顯影液)進行顯影。藉此,例如使用正型光阻時,經曝光的部分之光阻被除去,形成光阻之圖型。
作為顯影液,可舉出氫氧化鉀、氫氧化鈉等之鹼金屬氫氧化物的水溶液、氫氧化四甲基銨、氫氧化四乙基銨、膽鹼等氫氧化四級銨的水溶液、乙醇胺、丙基胺、乙二胺等胺水溶液等鹼性水溶液的例子。進一步可於這些顯影液中加入界面活性劑等。作為顯影之條件,可適宜地選自溫度5℃至50℃及時間10秒至600秒。
又,本發明中作為顯影液可使用有機溶劑。於曝光後藉由顯影液(溶劑)進行顯影。藉此,例如使用正型光阻時,除去未曝光的部分之光阻形成光阻之圖型。
作為顯影液,例如可舉出乙酸甲酯、乙酸丁酯、乙酸乙酯、乙酸異丙酯、乙酸戊酯、乙酸異戊酯、甲氧基乙酸乙酯、乙氧基乙酸乙酯、丙二醇單甲基醚乙酸酯、乙二醇單乙基醚乙酸酯、乙二醇單丙基醚乙酸酯、乙二醇單丁基醚乙酸酯、乙二醇單苯基醚乙酸酯、二乙二醇單甲基醚乙酸酯、二乙二醇單丙基醚乙酸酯、二乙二醇單乙基醚乙酸酯、二乙二醇單苯基醚乙酸酯、二乙二醇單丁基醚乙酸酯、2-甲氧基丁基乙酸酯、3-甲氧基丁基乙酸酯、4-甲氧基丁基乙酸酯、3-甲基-3-甲氧基丁基乙酸酯、3-乙基-3-甲氧基丁基乙酸酯、丙二醇單甲基醚乙酸酯、丙二醇單乙基醚乙酸酯、丙二醇單丙基醚乙酸酯、2-乙氧基丁基乙酸酯、4-乙氧基丁基乙酸酯、4-丙氧基丁基乙酸酯、2-甲氧基戊基乙酸酯、3-甲氧基戊基乙酸酯、4-甲氧基戊基乙酸酯、2-甲基-3-甲氧基戊基乙酸酯、3-甲基-3-甲氧基戊基乙酸酯、3-甲基-4-甲氧基戊基乙酸酯、4-甲基-4-甲氧基戊基乙酸酯、丙二醇二乙酸酯、甲酸甲酯、甲酸乙酯、甲酸丁酯、甲酸丙酯、乳酸乙酯、乳酸丁酯、乳酸丙酯、碳酸乙酯、碳酸丙酯、碳酸丁酯、丙酮酸甲酯、丙酮酸乙酯、丙酮酸丙酯、丙酮酸丁酯、乙醯乙酸甲酯、乙醯乙酸乙酯、丙酸甲酯、丙酸乙酯、丙酸丙酯、丙酸異丙酯、2-羥基丙酸甲酯、2-羥基丙酸乙酯、甲基-3-甲氧基丙酸酯、乙基-3-甲氧基丙酸酯、乙基-3-乙氧基丙酸酯、丙基-3-甲氧基丙酸酯等之例子。這些顯影液中可進一步添加界面活性劑等。作為顯影的條件,適宜地選自溫度5℃至50℃及時間10秒至600秒。
而將如此形成的光阻(上層)之圖型作為保護膜進行本發明之抗蝕下層膜(中間層)的除去,其次將由經圖型化的光阻及本發明之抗蝕下層膜(中間層)所成的膜作為保護膜,進行有機下層膜(下層)之除去。最後將經圖型化的本發明之抗蝕下層膜(中間層)及有機下層膜(下層)作為保護膜,進行半導體基板的加工。
首先,將除去光阻之部分的本發明之抗蝕下層膜(中間層)藉由乾蝕刻除去,露出半導體基板。於本發明之抗蝕下層膜的乾蝕刻中可使用四氟甲烷(CF4
)、全氟環丁烷(C4
F8
)、全氟丙烷(C3
F8
)、三氟甲烷、一氧化碳、氬、氧、氮、六氟化硫、二氟甲烷、三氟化氮及三氟化氯、氯、三氯硼烷及二氯硼烷等氣體。於抗蝕下層膜之乾蝕刻中使用鹵素系氣體者為佳。藉由鹵素系氣體之乾蝕刻中,基本上難以除去由有機物質所成的光阻。相對於此,含有大量矽原子之本發明的抗蝕下層膜可藉由鹵素系氣體而快速地除去。因此,可抑制抗蝕下層膜的乾蝕刻所造成的光阻之膜厚減少。而該結果為可將光阻使用在薄膜上。抗蝕下層膜的乾蝕刻以藉由氟系氣體者為佳,作為氟系氣體,例如可舉出四氟甲烷(CF4
)、全氟環丁烷(C4
F8
)、全氟丙烷(C3
F8
)、三氟甲烷,及二氟甲烷(CH2
F2
)等。
其後,由經圖型化的光阻及本發明之抗蝕下層膜所成的膜作為保護膜而進行有機下層膜的除去。有機下層膜(下層)藉由經氧系氣體的乾蝕刻進行者為佳。因含有大量矽原子之本發明的抗蝕下層膜再藉由氧系氣體的乾蝕刻中難以除去。
最後進行半導體基板之加工。半導體基板的加工以藉由經氟系氣體的乾蝕刻進行者為佳。
作為氟系氣體,例如可舉出四氟甲烷(CF4
)、全氟環丁烷(C4
F8
)、全氟丙烷(C3
F8
)、三氟甲烷,及二氟甲烷(CH2
F2
)等。
又,作為基板之加工可進行離子注入。 於基板加工後經由光罩層以含有過氧化氫之藥液進行除去之步驟而製造出半導體裝置。光罩層為含有抗蝕或抗蝕下層膜之有機下層膜。
又,於本發明之抗蝕下層膜的上層,於光阻形成前可形成有機系反射防止膜。於次作為使用的反射防止膜組成物並無特別限制,可使用任意選自至今慣用於光刻加工者,又慣用方法,例如可進行藉由旋塗器、塗布器之塗布及藉由燒成的反射防止膜之形成。
又,經本發明之抗蝕下層膜形成組成物塗布的基板可為於該表面上具有藉由CVD法等所形成的有機系或無機系之反射防止膜者,亦可為於該上面形成本發明之下層膜。
藉由本發明之抗蝕下層膜形成組成物所形成的抗蝕下層膜,又藉由光刻加工中所使用的光波長,有具有對該光之吸收性的情況。而於如此情況下,可作為具有防止自基板的反射光之效果的反射防止膜而發揮其功能。且,本發明之下層膜亦可作為以下的層使用,預防使基板與光阻之相互作用的層、使用於光阻之材料或具有防止光阻曝光時生成的物質對基板的壞作用之功能的層、於加熱燒成時具有防止自基板生成的物質對上層光阻的擴散之功能的層,及作為欲減少藉由半導體基板介電體層之光阻層的中毒效果(Poisoning effect)的障礙層等。
又,藉由抗蝕下層膜形成組成物所形成的抗蝕下層膜為,適用於形成在雙鑲嵌製程所使用的貫通孔之基板,可作為可無間隙下填充孔之填充材料使用。又,亦可作為欲使具有凹凸的半導體基板之表面進行平坦化的平坦化材料使用。
又,作為EUV抗蝕的下層膜,除作為硬光罩之功能以外,亦可使用於以下目的上。無需與EUV抗蝕互混,於EUV曝光(波長13.5nm)時可作為防止不佳的曝光之光,例如可作為防止自上述UV或DUV(ArF光、KrF光)的基板或界面之反射的EUV抗蝕之下層反射防止膜時,使用上述抗蝕下層膜形成組成物。可有效率地防止在EUV抗蝕的下層之反射。作為EUV抗蝕下層膜使用時,製程可與光阻用下層膜同様地進行。 [實施例]
<合成例1> 將四乙氧基矽烷20.0g、苯基三甲氧基矽烷1.5g、5-(三乙氧基矽基)六氫-4,7-甲醇異苯並呋喃-1,3-二酮14.6g、丙酮54.2g放入於300ml的燒瓶中,將混合溶液以磁力攪拌器一邊攪拌下,一邊將0.01M鹽酸水溶液9.7g滴入於混合溶液中。添加後,於調整為85℃的油浴中移入燒瓶,經240分鐘的迴流。其後,加入丙二醇單甲基醚乙酸酯72g,將丙酮、甲醇、乙醇、水進行減壓餾去,經濃縮得到水解縮合物(聚合物)水溶液。進一步添加丙二醇單乙基醚,作為丙二醇單乙基醚80%丙二醇單甲基醚乙酸酯20%的溶劑比率,以140℃中之固體殘物換算下調整至成13質量%。所得之聚合物相當於式(3-1),藉由GPC的重量平均分子量以聚苯乙烯換算為Mw1500。
<合成例2> 將四乙氧基矽烷20.0g、苯基三甲氧基矽烷1.5g、5-(三乙氧基矽基)六氫-4,7-甲醇異苯並呋喃-1,3-二酮14.6g、丙酮54.2g放入於300ml的燒瓶中,將混合溶液以磁力攪拌器一邊攪拌下,一邊將0.01M鹽酸水溶液9.7g滴入於混合溶液中。添加後,於調整為85℃的油浴中移入燒瓶,進行240分鐘之迴流。其後加入丙二醇單甲基醚乙酸酯72g,將丙酮、甲醇、乙醇、水進行減壓餾去,經濃縮後得到水解縮合物(聚合物)水溶液。再加入丙二醇單甲基醚,調整至在140℃中之固體殘物換算下成為13質量%。所得之聚合物相當於式(3-1),藉由GPC的重量平均分子量以聚苯乙烯換算為Mw1500。
<合成例3> 將四乙氧基矽烷19.3g、苯基三甲氧基矽烷1.4g、2,2,5-三甲基-5-(3-(三乙氧基矽基)丙基)-1,3-二噁烷-4,6-二酮15.5g、丙酮54.4g放入於300ml的燒瓶中,將混合溶液以磁力攪拌器一邊攪拌下,一邊將0.01M鹽酸水溶液9.4g滴入混合溶液中。添加後,於調整為85℃的油浴中移入燒瓶,進行240分鐘之迴流。其後加入丙二醇單甲基醚乙酸酯72g,將丙酮、甲醇、乙醇、水進行減壓餾去,經濃縮後得到水解縮合物(聚合物)水溶液。再加入丙二醇單乙基醚乙酸酯,作為丙二醇單乙基醚80%丙二醇單甲基醚乙酸酯20%的溶劑比率,調整至在140℃中之固體殘物換算下成為13質量%。所得之聚合物相當於式(3-2),藉由GPC的重量平均分子量以聚苯乙烯換算為Mw1500。
<合成例4> 將四乙氧基矽烷18.2g、苯基三甲氧基矽烷1.3g、二第三丁基2-(3-(三乙氧基矽基)丙基)丙二酸酯16.9g、丙酮54.4g放入於300ml的燒瓶中,將混合溶液以磁力攪拌器一邊攪拌下,將0.01M鹽酸水溶液8.8g滴入於混合溶液中。添加後,於調整為85℃的油浴中移入燒瓶,進行240分鐘之迴流。其後加入丙二醇單甲基醚乙酸酯72g,將丙酮、甲醇、乙醇、水進行減壓餾去,經濃縮後得到水解縮合物(聚合物)水溶液。再加入丙二醇單乙基醚,作為丙二醇單乙基醚80%丙二醇單甲基醚乙酸酯20%的溶劑比率,調整至在140℃中之固體殘物換算下成為13質量%。所得之聚合物相當於式(3-3),藉由GPC的重量平均分子量以聚苯乙烯換算為Mw1500。
<合成例5> 將四乙氧基矽烷20.6g、苯基三甲氧基矽烷1.5g、3-(3-(三乙氧基矽基)丙基)二氫呋喃-2,5-二酮13.9g、丙酮54.0g放入於300ml的燒瓶中,將混合溶液以磁力攪拌器一邊攪拌下,一邊將0.01M鹽酸水溶液10.0g滴入於混合溶液中。添加後,於調整為85℃的油浴中移入燒瓶,進行240分鐘之迴流。其後加入丙二醇單甲基醚乙酸酯72g,將丙酮、甲醇、乙醇、水進行減壓餾去,經濃縮後得到水解縮合物(聚合物)水溶液。再加入丙二醇單乙基醚,作為丙二醇單乙基醚80%丙二醇單甲基醚乙酸酯20%的溶劑比率,調整至在140℃中之固體殘物換算下成為13質量%。所得之聚合物相當於式(3-4),藉由GPC的重量平均分子量以聚苯乙烯換算為Mw1500。
<合成例6> 將四乙氧基矽烷24.1g、苯基三甲氧基矽烷1.6g、三乙氧基甲基矽烷4.42g、5-(三乙氧基矽基)六氫-4,7-甲醇異苯並呋喃-1,3-二酮5.4g、丙酮53.4g放入於300ml的燒瓶中,將混合溶液以磁力攪拌器一邊攪拌下,一邊將0.01M鹽酸水溶液11.0g滴入於混合溶液中。添加後,於調整為85℃的油浴中移入燒瓶,進行240分鐘之迴流。其後加入丙二醇單甲基醚72g,將丙酮、甲醇、乙醇、水進行減壓餾去,經濃縮後得到水解縮合物(聚合物)水溶液。再加入丙二醇單甲基醚,調整至在140℃中之固體殘物換算下成為13質量%。所得之聚合物相當於式(3-5),藉由GPC的重量平均分子量以聚苯乙烯換算為Mw1500。
<合成例7> 將四乙氧基矽烷12.1g、苯基三甲氧基矽烷1.3g、2,2,5-三甲基-5-(3-(三乙氧基矽基)丙基)-1,3-二噁烷-4,6-二酮23.4g、丙酮55.2g放入於300ml的燒瓶中,將混合溶液以磁力攪拌器一邊攪拌下,一邊將0.01M鹽酸水溶液8.0g滴入於混合溶液中。添加後,於調整為85℃的油浴中移入燒瓶,進行240分鐘之迴流。其後加入丙二醇單甲基醚74g,將丙酮、甲醇、乙醇、水進行減壓餾去,經濃縮後得到水解縮合物(聚合物)水溶液。再加入丙二醇單甲基醚,調整至在140℃中之固體殘物換算下成為13質量%。所得之聚合物相當於式(3-2),藉由GPC的重量平均分子量以聚苯乙烯換算為Mw1500。
<合成例8> 將四乙氧基矽烷19.5g、5-(三乙氧基矽基)六氫-4,7-甲醇異苯並呋喃-1,3-二酮14.2g、苯基磺醯基醯胺丙基三乙氧基矽烷2.6g、丙酮54.3g放入於300ml的燒瓶中,將混合溶液以磁力攪拌器一邊攪拌下,一邊將0.01M鹽酸水溶液9.5g滴入於混合溶液中。添加後,於調整為85℃的油浴中移入燒瓶,進行240分鐘之迴流。其後加入丙二醇單甲基醚72g,將丙酮、甲醇、乙醇、水進行減壓餾去,經濃縮後得到水解縮合物(聚合物)水溶液。再加入丙二醇單甲基醚,調整至在140℃中之固體殘物換算下成為13質量%。所得之聚合物相當於式(3-6),藉由GPC的重量平均分子量以聚苯乙烯換算為Mw1500。
<合成例9> 將四乙氧基矽烷17.2g、5-(三乙氧基矽基)六氫-4,7-甲醇異苯並呋喃-1,3-二酮13.6g、二烯丙基異氰酸酯丙基三乙氧基矽烷5.7g、丙酮54.7g放入於300ml的燒瓶中,將混合溶液以磁力攪拌器一邊攪拌下,一邊將0.01M鹽酸水溶液8.9g滴入於混合溶液。添加後,於調整為85℃的油浴中移入燒瓶,進行240分鐘之迴流。其後加入丙二醇單甲基醚72g,將丙酮、甲醇、乙醇、水進行減壓餾去,經濃縮後得到水解縮合物(聚合物)水溶液。再加入丙二醇單甲基醚,調整至在140℃中之固體殘物換算下成為13質量%。所得之聚合物相當於式(3-7),藉由GPC的重量平均分子量以聚苯乙烯換算為Mw1500。
<比較合成例1> 將四乙氧基矽烷24.1g、苯基三甲氧基矽烷1.8g、三乙氧基甲基矽烷9.5g、丙酮53.0g放入於300ml的燒瓶中,將混合溶液以磁力攪拌器一邊攪拌下,一邊將0.01M鹽酸水溶液11.7g滴入於混合溶液中。添加後,於調整為85℃的油浴中移入燒瓶,進行240分鐘之迴流。其後添加丙二醇單甲基醚70g,將丙酮、甲醇、乙醇、水進行減壓餾去,經濃縮後得到水解縮合物(聚合物)水溶液。再加入丙二醇單甲基醚,調整至在140℃中之固體殘物換算下成為13質量%。所得之聚合物相當於式(4-1),藉由GPC的重量平均分子量以聚苯乙烯換算為Mw1400。
<Si含有抗蝕下層膜之調整> 在上述合成例1至合成例9、比較合成例1所得之含矽聚合物、酸、溶劑以表1所示比例進行混合,藉由0.1μm的氟樹脂製濾器進行過濾後,各調製出含有聚合物之塗布液。表1中之聚合物的添加比例並非聚合物溶液之添加量,其表示聚合物本身的添加量。
在表1中,MA表示馬來酸,TPSNO3表示三苯基硫鎓硝酸鹽,TPSTFA表示三苯基硫鎓三氟乙酸鹽,TPSML表示三苯基硫鎓馬來酸鹽,BPS表示雙酚碸,PGEE表示丙二醇單乙基醚及PGMEA表示丙二醇單甲基醚乙酸酯。各添加量表示質量份。
<有機下層膜A之調整> 在氮氣下,於100mL四口燒瓶中放入咔唑(6.69g、0.040 mol、東京化成工業(股)製)、9-芴酮(7.28g、0.040 mol、東京化成工業(股)製)、對甲苯磺酸一水合物(0.76g、0.0040 mol、東京化成工業(股)製),放入1,4-二噁烷(6.69g、關東化學(股)製)並攪拌,升溫至100℃使其溶解而開始聚合。經24小時後,冷卻至60℃後,加入氯仿(34g、關東化學(股)製)使其稀釋,於甲醇(168g、關東化 學(股)製)再沈澱。過濾所得之沈澱物,以減壓乾燥機進行80℃之24小時乾燥,得到目的之聚合物(式(5-1),以下簡稱為PCzFL)9.37g。PCzFL的1
H-NMR之測定結果如以下所示。1
H-NMR(400MHz, DMSO-d6
):δ7.03-7.55(br, 12H), δ7.61-8.10(br, 4H), δ11.18(br, 1H) PCzFL藉由GPC以聚苯乙烯換算所測定的重量平均分子量Mw為2800,多分散度Mw/Mn為1.77。 於所得之樹脂20g中,混合作為交聯劑之四甲氧基甲基乙二醇脲(Mitsui Cytec(股)製之商品名Powder link1174) 3.0g、作為觸媒之吡啶鎓對甲苯磺酸鹽0.30g、作為界面活性劑之MegafacR-30(大日本油墨化學(股)製之商品名)0.06g,溶解於丙二醇單甲基醚乙酸酯88g中成為溶液。其後,使用孔徑0.10μm的聚乙烯製微過濾器進行過濾,再使用孔徑0.05μm之聚乙烯製微過濾器進行過濾,調製出使用於藉由多層膜之光刻加工的有機下層膜(A層)形成組成物之溶液。
[藉由ArF曝光之抗蝕圖型評估:PTD] <抗蝕製圖評估:進行鹼顯影之經由PTD步驟的評估> 將以上述式所得之有機下層膜(A層)形成組成物塗布於矽晶圓上,以加熱板上進行240℃的60秒燒烤,得到膜厚200nm之有機下層膜(A層)。於該上面,塗布在實施例3,實施例4,實施例6至實施例10、比較例1所得之含有Si的抗蝕下層膜(B層)形成組成物,在加熱板上進行180℃之60秒燒烤,得到含有Si的抗蝕下層膜(B層)。含有Si的抗蝕下層膜(B層)之膜厚為40nm。 於B層上面將市售的ArF用抗蝕溶液(JSR(股)製之商品名:AR2772JN)藉由旋塗器進行各塗布,在加熱板上進行110℃的1分鐘加熱,形成膜厚120nm之光阻膜(C層)。 使用(股)Nikon製NSR-S307E掃描器(波長193nm、NA、σ:0.85、0.93/0.85),於顯影後,各通過經設定的光罩進行曝光至光阻的線寬及其線間的寬成為0.062μm,即形成0.062μm的線和空間(L/S)=1/1之密集的線條。其後,在加熱板上進行100℃的60秒燒烤,冷卻後使用2.38%鹼水溶液進行60秒顯影,於抗蝕下層膜(B層)上形成正型圖型。對於所得之光阻圖型,若無產生過大圖型剝落或底切、線底部的寬厚(Footing)者評估為良好。
[藉由ArF曝光之抗蝕圖型評估:NTD] <抗蝕製圖評估:進行溶劑顯影經由NTD步驟的評估> 將以上述式所得之有機下層膜(A層)形成組成物塗布於矽晶圓上,在加熱板上進行240℃的60秒燒烤,得到膜厚200nm之有機下層膜(A層)。於該上面,塗布在實施例1至實施例7、比較例1所得之含有Si的抗蝕下層膜(B層)形成組成物,在加熱板上進行180℃的60秒燒烤,得到含有Si的抗蝕下層膜(B層)。含有Si的抗蝕下層膜(B層)之膜厚為40nm。 於B層的上面將市售的光阻溶液(FUJIFILM Corporation(股)製之商品名FAiRS-9521NT05)藉由旋塗器各進行塗布,在加熱板上進行100℃的1分鐘加熱,形成膜厚85nm之光阻膜(C層)。 使用(股)Nikon製NSR-S307E掃描器(波長193nm、NA、σ:0.85、0.93/0.85),於顯影後各通過經設定的光罩而進行曝光至光阻的線寬及其線間的寬成為0.062μm,即形成0.062μm的線和空間(L/S)=1/1之密集的線條。其後在加熱板上進行100℃的60秒燒烤,冷卻後使用2.38%鹼水溶液進行60秒顯影,於抗蝕下層膜(B層)上面形成正型圖型。對於所得之光阻圖型,若無產生過大圖型剝落或底切、線底部的寬厚(Footing)者評估為良好。
[藉由SC-1藥液(含有氨與過氧化氫之水溶液)之除去性評估] 將在實施例1至實施例10、比較例1所調製之含有Si的塗布液使用旋塗器,塗布於矽晶圓上。在加熱板上進行180℃的1分鐘加熱,各形成含有Si的抗蝕下層膜。其後,將調整為60℃的SC-1藥液(28%氨水/33%過氧化氫水/水=1/1/40)在含有Si的抗蝕下層膜上進行3分鐘塗布,進行1分鐘水輕洗(rinse)後再進行30秒旋轉乾燥,評估在溶劑塗布前後有無膜厚變化。膜厚變化若為90%以上者評估為「良好」,若膜厚變化為90%以下者評估為「未溶解」。
[O2
蝕刻後藉由SC-1藥液的除去性評估] 將在實施例1至實施例10、比較例1所調製的含有Si之塗布液,使用旋塗器塗布於矽晶圓上。在加熱板上進行180℃的1分鐘加熱,各形成含有Si的抗蝕下層膜。其後使用Samko製乾蝕刻器(RIE-10NR),進行5秒氧蝕刻。其後將調整為60℃的SC-1藥液(28%氨水/33%過氧化氫水/水=1/1/40)於含有Si的抗蝕下層膜上進行3分鐘塗布,進行1分鐘水輕洗(rinse),再進行30秒旋轉乾燥,評估溶劑塗布前後的有無膜厚變化。膜厚變化為90%以上者評估為「良好」,膜厚變化為90%以下者評估為「未溶解」。[產業上可利用性]
本發明為作為ArF、KrF、EUV的抗蝕下層膜而形成良好圖型上為有用,且無需將光刻後的光罩殘渣進行蝕刻下可藉由藥液除去,對基板的損傷為少。在光刻步驟欲於下層轉印圖型而介著光罩進行蝕刻時,即使為經蝕刻後的光罩,亦可將殘渣光罩除去時以藥液除去。
Claims (15)
- 一種含矽抗蝕下層膜形成組成物,其為欲形成含矽抗蝕下層膜的組成物,其特徵為該含矽抗蝕下層膜為,在以光刻加工將圖型轉印於下層後,以含有過氧化氫之藥液進行光罩層的除去之步驟中,作為該光罩層而使用的膜,前述組成物為含有具有單位結構的聚矽氧烷,該單位結構為具有含有羰基之官能基。
- 如請求項1之含矽抗蝕下層膜形成組成物,其中具有含有羰基之官能基之單位結構為含有環狀酸酐基、環狀二酯基,或二酯基之單位結構。
- 如請求項1之含矽抗蝕下層膜形成組成物,其中前述聚矽氧烷為含有下述式(1)所示矽烷之水解性矽烷的水解縮合物; 式(1):[式(1)中,R1 為包含式(1-1)、式(1-2)、式(1-3)、式(1-4)、式(1-5),或式(1-6):(式中,T1 、T4 表示伸烷基或環狀伸烷基,T2 表示烷基,T3 表示各環狀伸烷基;n表示1或2的整數;T11 、T15 及T18 表示伸烷基、環狀伸烷基、伸烯基、伸芳基、硫原子、氧原子、氧羰基、醯胺基、2級胺基,或此等組合,T12 、T13 、T14 、T16 、T17 、T19 及T20 各表示氫原子或烷基,T21 表示伸烷基;※表示直接或經由連結基與矽原子之鍵結部位)之有機基,且藉由Si-C鍵與矽原子鍵結者; 式(1)中,R2 表示烷基、芳基、鹵化烷基、鹵化芳基、烯基,或具有環氧基、丙烯醯基、甲基丙烯醯基、巰基、胺基,或者氰基的有機基,且藉由Si-C鍵與矽原子鍵結者; 式(1)中,R3 表示烷氧基、醯氧基,或鹵素原子;a表示1的整數,b表示0或1的整數,a+b表示1或2的整數]。
- 如請求項1或2之含矽抗蝕下層膜形成組成物,其中前述聚矽氧烷為進一步含有具有有機基的單位結構,該有機基為含有醯胺基者。
- 如請求項4之含矽抗蝕下層膜形成組成物,其中醯胺基為磺醯胺基,或二烯丙基異氰脲酸酯基。
- 如請求項1之含矽抗蝕下層膜形成組成物,其中前述聚矽氧烷為含有前述式(1)所示矽烷及下述式(2)所示矽烷之水解性矽烷的共水解縮合物; 式(2):[式(2)中,R4 表示含有式(2-1),或式(2-2):之有機基,且藉由Si-C鍵與矽原子鍵結者; 式(2)中,R5 表示烷基、芳基、鹵化烷基、鹵化芳基、烯基,或具有環氧基、丙烯醯基、甲基丙烯醯基、巰基、胺基,或者氰基之有機基,且藉由Si-C鍵與矽原子鍵結者; 式(2)中,R6 表示烷氧基、醯氧基,或鹵素原子;a表示1的整數,b表示0或1的整數,a+b表示1或2的整數;※表示直接或經由連結基與矽原子之鍵結部位]。
- 如請求項1之含矽抗蝕下層膜形成組成物,其中前述聚矽氧烷為含有前述式(1)所示矽烷、前述式(2)所示矽烷與其他矽烷的水解性矽烷之共水解縮合物,其他矽烷為選自由式(3)所示矽烷及式(4)所示矽烷所成群的至少1種矽烷;(式(3)中,R7 表示烷基、芳基、鹵化烷基、鹵化芳基、烯基,或具有環氧基、丙烯醯基、甲基丙烯醯基、巰基,或者氰基之有機基,且藉由Si-C鍵與矽原子鍵結者,R8 表示烷氧基、醯氧基,或鹵素原子,a表示0至3的整數);(式(4)中,R9 表示烷基,且藉由Si-C鍵與矽原子鍵結者,R10 表示烷氧基、醯氧基,或鹵素基,Y表示伸烷基或伸芳基,b表示0或1的整數,c表示0或1的整數)。
- 如請求項1至請求項7中任1項之含矽抗蝕下層膜形成組成物,其中進一步含有光酸產生劑。
- 如請求項1至請求項8中任1項之含矽抗蝕下層膜形成組成物,其中進一步含有金屬氧化物。
- 如請求項1至請求項9中任1項之含矽抗蝕下層膜形成組成物,其中前述含有過氧化氫之藥液為,含有氨與過氧化氫之水溶液、含有鹽酸與過氧化氫之水溶液、含有硫酸與過氧化氫之水溶液,或含有氫氟酸與過氧化氫之水溶液。
- 一種抗蝕下層膜的製造方法,其特徵為藉由將如請求項1至請求項10中任1項之抗蝕下層膜形成組成物塗布於半導體基板上後進行燒成而得者。
- 一種半導體裝置的製造方法,其特徵含有將如請求項1至請求項10中任1項之抗蝕下層膜形成組成物塗布於半導體基板上後進行燒成而形成抗蝕下層膜之步驟、於前述下層膜上塗布抗蝕用組成物而形成抗蝕膜之步驟、使前述抗蝕膜進行曝光之步驟、於曝光後使抗蝕進行顯影而得到抗蝕圖型之步驟、藉由抗蝕圖型使抗蝕下層膜進行蝕刻的步驟,及藉由經圖型化的抗蝕與抗蝕下層膜,加工半導體基板之步驟、將光罩層以含有過氧化氫之藥液進行除去之步驟。
- 一種半導體裝置之製造方法,其特徵為含有於半導體基板上形成有機下層膜之步驟、於其上塗布如請求項1至請求項10中任1項之抗蝕下層膜形成組成物,並燒成後形成抗蝕下層膜之步驟、於前述抗蝕下層膜上塗布抗蝕用組成物而形成抗蝕層之步驟、使前述抗蝕膜進行曝光之步驟、於曝光後使抗蝕進行顯影而得到抗蝕圖型之步驟、藉由抗蝕圖型使抗蝕下層膜進行蝕刻的步驟、藉由經圖型化之抗蝕下層膜使有機下層膜進行蝕刻的步驟,及藉由經圖型化的有機下層膜,加工半導體基板之步驟、將光罩層以含有過氧化氫的藥液進行除去之步驟。
- 如請求項12或13之半導體裝置之製造方法,其中前述基板之加工為蝕刻,或離子注入。
- 如請求項12或13之半導體裝置之製造方法,其中光罩層為含有抗蝕或抗蝕下層膜之有機下層膜。
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