TWI585537B - 膜形成組成物及離子注入方法 - Google Patents
膜形成組成物及離子注入方法 Download PDFInfo
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- TWI585537B TWI585537B TW102105608A TW102105608A TWI585537B TW I585537 B TWI585537 B TW I585537B TW 102105608 A TW102105608 A TW 102105608A TW 102105608 A TW102105608 A TW 102105608A TW I585537 B TWI585537 B TW I585537B
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- ion implantation
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- HMNFSPVCKZFHGZ-UHFFFAOYSA-N bis(4-ethenoxybutyl) benzene-1,4-dicarboxylate Chemical compound C=COCCCCOC(=O)C1=CC=C(C(=O)OCCCCOC=C)C=C1 HMNFSPVCKZFHGZ-UHFFFAOYSA-N 0.000 description 1
- JZQAAQZDDMEFGZ-UHFFFAOYSA-N bis(ethenyl) hexanedioate Chemical compound C=COC(=O)CCCCC(=O)OC=C JZQAAQZDDMEFGZ-UHFFFAOYSA-N 0.000 description 1
- 150000001621 bismuth Chemical class 0.000 description 1
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- ZAZUOXBHFXAWMD-UHFFFAOYSA-N butyl 2-oxopropanoate Chemical compound CCCCOC(=O)C(C)=O ZAZUOXBHFXAWMD-UHFFFAOYSA-N 0.000 description 1
- DFFDSQBEGQFJJU-UHFFFAOYSA-M butyl carbonate Chemical compound CCCCOC([O-])=O DFFDSQBEGQFJJU-UHFFFAOYSA-M 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 1
- 229960001231 choline Drugs 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- FHIVAFMUCKRCQO-UHFFFAOYSA-N diazinon Chemical compound CCOP(=S)(OCC)OC1=CC(C)=NC(C(C)C)=N1 FHIVAFMUCKRCQO-UHFFFAOYSA-N 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
- UYAAVKFHBMJOJZ-UHFFFAOYSA-N diimidazo[1,3-b:1',3'-e]pyrazine-5,10-dione Chemical compound O=C1C2=CN=CN2C(=O)C2=CN=CN12 UYAAVKFHBMJOJZ-UHFFFAOYSA-N 0.000 description 1
- 238000007922 dissolution test Methods 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 1
- CKSRFHWWBKRUKA-UHFFFAOYSA-N ethyl 2-ethoxyacetate Chemical compound CCOCC(=O)OCC CKSRFHWWBKRUKA-UHFFFAOYSA-N 0.000 description 1
- JLEKJZUYWFJPMB-UHFFFAOYSA-N ethyl 2-methoxyacetate Chemical compound CCOC(=O)COC JLEKJZUYWFJPMB-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- MNWFXJYAOYHMED-UHFFFAOYSA-M heptanoate Chemical compound CCCCCCC([O-])=O MNWFXJYAOYHMED-UHFFFAOYSA-M 0.000 description 1
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- XEMZLVDIUVCKGL-UHFFFAOYSA-N hydrogen peroxide;sulfuric acid Chemical compound OO.OS(O)(=O)=O XEMZLVDIUVCKGL-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229940117955 isoamyl acetate Drugs 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 229940011051 isopropyl acetate Drugs 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
- HSDFKDZBJMDHFF-UHFFFAOYSA-N methyl 3-ethoxypropanoate Chemical compound CCOCCC(=O)OC HSDFKDZBJMDHFF-UHFFFAOYSA-N 0.000 description 1
- CWKLZLBVOJRSOM-UHFFFAOYSA-N methyl pyruvate Chemical compound COC(=O)C(C)=O CWKLZLBVOJRSOM-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- CQDGTJPVBWZJAZ-UHFFFAOYSA-N monoethyl carbonate Chemical compound CCOC(O)=O CQDGTJPVBWZJAZ-UHFFFAOYSA-N 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 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
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000656 polylysine Polymers 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 1
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 1
- 239000001818 polyoxyethylene sorbitan monostearate Substances 0.000 description 1
- 235000010989 polyoxyethylene sorbitan monostearate Nutrition 0.000 description 1
- 239000001816 polyoxyethylene sorbitan tristearate Substances 0.000 description 1
- 235000010988 polyoxyethylene sorbitan tristearate Nutrition 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- ILVGAIQLOCKNQA-UHFFFAOYSA-N propyl 2-hydroxypropanoate Chemical compound CCCOC(=O)C(C)O ILVGAIQLOCKNQA-UHFFFAOYSA-N 0.000 description 1
- ILPVOWZUBFRIAX-UHFFFAOYSA-N propyl 2-oxopropanoate Chemical compound CCCOC(=O)C(C)=O ILPVOWZUBFRIAX-UHFFFAOYSA-N 0.000 description 1
- JCMFJIHDWDKYIL-UHFFFAOYSA-N propyl 3-methoxypropanoate Chemical compound CCCOC(=O)CCOC JCMFJIHDWDKYIL-UHFFFAOYSA-N 0.000 description 1
- FOWDZVNRQHPXDO-UHFFFAOYSA-N propyl hydrogen carbonate Chemical compound CCCOC(O)=O FOWDZVNRQHPXDO-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 229940116423 propylene glycol diacetate Drugs 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 150000004060 quinone imines Chemical group 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229940035044 sorbitan monolaurate Drugs 0.000 description 1
- 239000001593 sorbitan monooleate Substances 0.000 description 1
- 235000011069 sorbitan monooleate Nutrition 0.000 description 1
- 229940035049 sorbitan monooleate Drugs 0.000 description 1
- 239000001587 sorbitan monostearate Substances 0.000 description 1
- 235000011076 sorbitan monostearate Nutrition 0.000 description 1
- 229940035048 sorbitan monostearate Drugs 0.000 description 1
- 239000001589 sorbitan tristearate Substances 0.000 description 1
- 235000011078 sorbitan tristearate Nutrition 0.000 description 1
- 229960004129 sorbitan tristearate Drugs 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- DVUVKWLUHXXIHK-UHFFFAOYSA-N tetraazanium;tetrahydroxide Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[OH-].[OH-].[OH-].[OH-] DVUVKWLUHXXIHK-UHFFFAOYSA-N 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- 239000010409 thin film Substances 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
- KDQYHGMMZKMQAA-UHFFFAOYSA-N trihexyl borate Chemical compound CCCCCCOB(OCCCCCC)OCCCCCC KDQYHGMMZKMQAA-UHFFFAOYSA-N 0.000 description 1
- GCMBIWYUVPAPEG-UHFFFAOYSA-N tris(1,1,1,3,3,3-hexafluoropropan-2-yl) borate Chemical compound FC(F)(F)C(C(F)(F)F)OB(OC(C(F)(F)F)C(F)(F)F)OC(C(F)(F)F)C(F)(F)F GCMBIWYUVPAPEG-UHFFFAOYSA-N 0.000 description 1
- JOAZIIBFQMIXJM-UHFFFAOYSA-N tris(4-chlorophenyl) borate Chemical compound C1=CC(Cl)=CC=C1OB(OC=1C=CC(Cl)=CC=1)OC1=CC=C(Cl)C=C1 JOAZIIBFQMIXJM-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
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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
-
- 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
- H01L21/26566—Bombardment with radiation with high-energy radiation producing ion implantation of a cluster, e.g. using a gas cluster ion beam
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/04—Esters of boric acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
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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
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
- C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
-
- 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
-
- 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
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/40—Treatment after imagewise removal, e.g. baking
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
- H01J37/30—Electron-beam or ion-beam tubes for localised treatment of objects
- H01J37/317—Electron-beam or ion-beam tubes for localised treatment of objects for changing properties of the objects or for applying thin layers thereon, e.g. for ion implantation
- H01J37/3171—Electron-beam or ion-beam tubes for localised treatment of objects for changing properties of the objects or for applying thin layers thereon, e.g. for ion implantation for ion implantation
-
- 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
- H01L21/26506—Bombardment with radiation with high-energy radiation producing ion implantation in group IV semiconductors
- H01L21/26526—Recoil-implantation
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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
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
- H01L21/3115—Doping the insulating layers
- H01L21/31155—Doping the insulating layers by ion implantation
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- High Energy & Nuclear Physics (AREA)
- Organic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Computer Hardware Design (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
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- Toxicology (AREA)
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- Architecture (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Materials For Photolithography (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polyethers (AREA)
- Epoxy Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本發明係關於一種於基板注入離子之際,用以將所欲之離子種導入該基板之透過形成於該基板上之離子注入用膜的離子注入方法。再者,本發明係關於用以形成該離子注入用膜及光阻下層膜的組成物。
於半導體元件之製造中,例如,採用以光阻圖型作為光罩,於半導體基板,將賦予n型或p型之導電型之雜質離子導入的離子注入。於該場合,前述雜質離子,係使用離子注入裝置(離子摻合裝置),於半導體基板,直接、或透過形成於該半導體基板之表面的薄膜注入。之後,前述光阻圖型,例如,係藉由以硫酸-過氧化氫水之晶圓洗淨、以氨水-過氧化氫水之晶圓洗淨、或灰化來除去。
然而,已知於半導體基板上塗佈抗反射膜形成組成物,藉由烘烤形成抗反射膜(光阻下層膜),於其上形成光阻圖型,藉此,可使該光阻圖型形成為所欲之形狀(例如,專利文獻1)。又,亦已知由含有含磷原子之高分子
化合物之組成物所形成的抗反射膜(專利文獻2)。磷原子,係n型半導體所含之供體的代表例。然而,如前述之透過抗反射膜於半導體基板離子注入並非較佳。其理由在於,前述抗反射膜中所含之雜質會侵入前述半導體基板,故有對所製作之半導體元件之特性造成影響之虞之故。
專利文獻1:國際公開第2005/098542號
專利文獻2:日本特開2004-205900號公報
通常,於半導體元件之製程中用以進行離子注入之光阻圖型的形成,係使用光阻及光阻上層膜(上層抗反射膜)。然而,隨著光阻圖型的微細化,為了形成該光阻圖型,取代光阻上層膜而光阻下層膜之必要性增加。不透過光阻下層膜之於基板注入離子時,必須將被覆該基板之離子注入部的前述光阻下層膜,蝕刻除去。或者,採用於顯像液中可溶性者作為該光阻下層膜,而必須以顯像液溶解被覆該離子注入部的前述光阻下層膜以除去。一般而言,希望以不較以往增加步驟數、更佳為較以往少之步驟,製作半導體元件。
本發明之目的在於,提供一種於適用於半導體元件之製作,不將前述光阻下層膜蝕刻除去或溶解於顯像液除去之離子注入方法,亦即,透過形成於基板上之離子注入用膜之離子注入方法,以及提供用以形成該膜之組成物。
另一方面,於半導體製程中,調整光阻之感度為重要。光阻之感度高時,以少曝光量即可形成所欲之光阻圖型。亦即以短曝光時間步驟即結束,故可期盼生產量的提升。相反的,當光阻感度低時,需要高曝光量,相反的由於光阻圖型形狀對於些許之曝光量變化的變化小,故有廣泛取得製程邊際的優點。通常,當由光阻以外之材料調整光阻的感度時,例如由光阻下層膜調整光阻的感度時,係使用下述手法:藉由使添加有酸產生物質及鹼性物質之光阻下層膜中之該等添加物質移行至光阻中,以調整光阻內所產生之酸的強度。然而,由光阻下層膜使酸產生物質及鹼性物質移行的手法,於光阻中會產生來自光阻下層膜成分之濃度梯度,故於與光阻下層膜之界面側感度變化的效果會大幅顯現,而成為使光阻形狀之基蝕及摺邊形狀產生的原因。
本發明之另一目的在於提供一種可由光阻下層膜調整光阻之感度之光阻下層膜形成組成物。
本發明人,為了解決前述課題而努力進行探討的結果發現,藉由透過使用本發明之離子注入用膜形成組成物所形成之膜於基板注入離子,可將前述膜中之所欲之元素導入該基板中。
亦即,本發明之第一樣態,係一種離子注入方法,其係含有:將含有含13族、14族、15族或16族之元素的
化合物及有機溶劑的膜形成組成物,塗佈於基板上烘烤而形成膜之步驟、將雜質離子由前述膜之上方介由前述膜而注入前述基板,且同時將前述膜中之13族、14族、15族或16族之元素導入前述基板中之步驟。
前述離子注入方法,於前述形成膜之步驟之後、將前述雜質離子注入前述基板之前,亦可包含於該膜上形成光阻圖型之步驟。
前述雜質離子之離子種為硼、磷、砷、碳、氮、氧、氟、氬、矽、鎵、鍺、銦、銻。
再者,前述含13族、14族、15族或16族之元素的化合物係含有選自由硼、鋁、鎵、碳、矽、鍺、氮、磷、砷、氧、硫及硒所構成之群中之至少一種的化合物。
本發明之第2樣態,係一種組成物,其係含有含13族、14族、15族或16族之元素的化合物及有機溶劑的離子注入用膜形成組成物,前述含13族、14族、15族或16族之元素之化合物係含有選自由硼、鋁、鎵、碳、矽、鍺、氮、磷、砷、氧、硫及硒所構成之群中之至少一種的化合物,該化合物之中,含有選自由碳、氮、氧及硫所構成之群中之至少一種之化合物係具有(甲基)丙烯醯基之化合物、具有(甲基)丙烯醯基之化合物的聚合物或共聚物、具有乙烯基之化合物、具有乙烯基之化合物的聚合物或共聚物、具有-C(=O)-O-基之化合物、具有-S-S-(disufide)基之化合物、具有三嗪環或三嗪三酮環之化合物、酚醛清
漆、咔唑酚醛清漆、聚醯胺酸或聚醯亞胺。
含有前述至少一種的化合物,並不限定於聚合物,可為單體、亦可為寡聚物。
本發明之第3樣態,係一種光阻下層膜形成組成物,其特徵係,含有下述式(0)所表示之化合物:
(式中,R表示碳原子數1~20之烷基、矽基、碳原子數1~20之鹵烷基、或可以碳原子數1~6之烷基、碳原子數1~6之鹵烷基及鹵素基之至少一種取代之苯基、萘基或蒽基,X表示亦可以鹵素基取代之碳原子數1~20之烷基、乙烯基、烯丙基、羥基、羧基、胺基、碳原子數1~20之烷硫基、氰基、乙醯基、乙醯氧基、碳原子數2~20之烷氧羰基、硝基、亞硝基、醯胺基、醯亞胺基、碳原子數1~20之烷氧磺醯基、磺醯胺基、或可以碳原子數1~6之烷基、碳原子數1~6之鹵烷基及鹵素基之至少一種取代之苯基、萘基、蒽基或芘基,p表示2或3)。
本說明書中,鹵素基,可舉例如氟基、氯基、溴基、碘基。又,所謂鹵烷基,係指烷基之至少1個氫原子以前述鹵素基取代之基。
藉由透過使用本發明之離子注入用膜形成組成物於基板所形成之膜於該基板注入離子,可於同一步驟進行將雜質離子注入該基板、與將該膜中之所欲之元素導入該基板中。
此外,當該離子注入方法包含形成光阻圖型之步驟時,本發明之光阻下層膜形成組成物,特別適於作為形成該光阻圖型之際所使用之組成物。藉由使用本發明之光阻下層膜形成組成物,即使不於該光阻下層膜形成組成物中添加酸產生物質及鹼性物質,亦可對光阻賦予感度變化的效果,並且,光阻之下緣形狀不會變成基蝕及摺邊形狀,可得矩形之光阻圖型。
圖1,係顯示離子注入後之基板內之碳濃度分布之圖。
圖2,係顯示離子注入後之基板內之氮濃度分布之圖。
圖3,係顯示離子注入後之基板內之磷濃度分布之圖。
圖4,係顯示離子注入後之基板內之硫濃度分布之圖。
圖5,係顯示離子注入後之基板內之硼濃度分布之圖。
圖6,係顯示離子注入後之基板內之碳濃度分布之圖。
圖7,係顯示離子注入後之基板內之磷濃度分布之圖。
圖8,係顯示離子注入後之基板內之硼濃度分布之圖。
圖9,由攝影由實施例8之光阻下層膜形成組成物所形成之光阻下層膜上之光阻圖型之截面之SEM影像。
圖10,係攝影由比較例3之光阻下層膜形成組成物所形成之光阻下層膜上之光阻圖型之截面之SEM影像。
圖11,係攝影於矽晶圓上不設置光阻下層膜所形成之光阻圖型之截面之SEM影像。
說明本發明之離子注入方法。
於基板上,藉由旋轉器、塗佈器等適當之塗佈方法,塗佈含有含13族、14族、15族或16族之元素的化合物及有機溶劑的膜形成組成物,之後,使用加熱板等加熱手段進行烘烤使其硬化而形成膜。
前述烘烤條件,係由烘烤溫度80℃至400℃、烘烤時間0.3分鐘至10分鐘之中適當地加以選擇。
再者,前述基板,可舉例如,矽晶圓(該矽晶圓之表面亦可以氧化矽膜、氮化矽膜、氧化氮化矽膜、或結晶質或非晶質之半導體膜被覆)、及形成有結晶質或非晶質之
半導體膜之氮化矽基板、石英基板或玻璃基板(含無鹼玻璃、低鹼玻璃、結晶化玻璃)、及氮化鎵、砷化鎵、硒化鋅等之化合物半導體基板。
經由前述步驟於基板上所形成之膜上,係視需要形成光阻圖型。為了形成前述光阻圖型,首先,於前述膜上形成光阻膜。前述光阻膜之形成,可藉由一般方法,亦即光阻溶液之塗佈及烘烤進行。
前述光阻溶液,只要能感光曝光光束者即可,並無特別限定。可舉例如,酚醛清漆樹脂與1,2-萘酚醌二疊氮磺酸酯所構成之正型光阻、含羥基之聚合物、胺基塑料交聯劑、於光酸產生劑所構成之系藉由酸交聯以使鹼溶解速度下降之負型光阻、具有藉由酸分解而使鹼溶解速度上升之基之黏結劑與光酸產生劑所構成之化學增幅型光阻、藉由酸而分解以使光阻之鹼溶解速度上升之低分子化合物與鹼可溶性黏結劑與光酸產生劑所構成之化學增幅型光阻、具有藉由酸分解而使鹼溶解速度上升之基之黏結劑與藉由酸而分解以使光阻之鹼溶解速度上升之低分子化合物與光酸產生劑所構成之化學增幅型光阻。亦可取代前述光阻,而使用感應電子線或EUV(極紫外線)之光阻。
於形成光阻圖型之際,曝光係透過用以形成既定圖型之光罩(網線)進行。於曝光時,可使用例如g線、i線、KrF準分子雷射、ArF準分子雷射、EUV、電子線。曝光後,可視需要進行曝光後加熱(Post Exposure Bake)。
曝光後加熱之條件,可由加熱溫度80℃至150℃、加
熱時間0.3分鐘至60分鐘之中適當地加以選擇。
對形成有光阻膜之半導體基板,使用光罩(網線)進行曝光,之後以鹼性顯像液或有機溶劑顯像。
前述鹼性顯像液,可舉例如,氫氧化鉀、氫氧化鈉等鹼金屬氫氧化物之水溶液、氫氧化四甲基銨、氫氧化四乙基銨、膽鹼等氫氧化四級銨之水溶液、乙醇胺、丙胺、乙二胺等胺水溶液。再者,亦可於該等鹼性顯像液添加界面活性劑。
使用該等鹼性顯像液之顯像的條件,可由顯像溫度5℃至50℃、顯像時間10秒鐘至300秒鐘之中適當地加以選擇。
當使用有機溶劑進行顯像時,該有機溶劑,可舉例如,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、丙二醇單甲醚乙酸酯、乙二醇單乙醚乙酸酯、乙二醇單丙醚乙酸酯、乙二醇單丁醚乙酸酯、乙二醇單苯醚乙酸酯、二乙二醇單甲醚乙酸酯、二乙二醇單丙醚乙酸酯、二乙二醇單乙醚乙酸酯、二乙二醇單苯醚乙酸酯、二乙二醇單丁醚乙酸酯、二乙二醇單乙醚乙酸酯、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、丙二醇單甲醚乙酸酯、丙二醇單乙醚乙酸酯、丙二醇單丙醚乙酸酯、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。再者,亦可於該等有機溶劑添加界面活性劑。
使用該等有機溶劑之顯像的條件,可由顯像溫度5℃至50℃、顯像時間10秒鐘至600秒鐘之中適當地加以選擇。
之後,使用周知之離子注入裝置或離子摻雜裝置,由前述膜之上方將雜質離子透過該膜注入前述基板。此時,前述膜中之13族、14族、15族或16族之元素被導入該基板中。當於前述膜上形成有光阻圖型時,前述雜質離子,會被注入該光阻圖型,故被光阻圖型被覆的部分實質上並無注入。
離子注入條件,可由加速電壓:500eV至10MeV、劑量:1×1010/cm2至1×1018/cm2之範圍選擇適當的條件。
用以於基板上形成膜的前述膜形成組成物係含有含13族、14族、15族或16族之元素的化合物及有機溶劑
的離子注入用膜形成組成物,例如,係含有含選自由硼、鋁、鎵、碳、矽、鍺、氮、磷、砷、氧、硫及硒所構成之群中之至少1種之化合物、及有機溶劑的離子注入用膜形成組成物。
前述離子注入用膜形成組成物所含之含選自由硼、鋁、鎵、碳、矽、鍺、氮、磷、砷、氧、硫及硒所構成之群中之至少1種之化合物,可舉例如,具有(甲基)丙烯醯基之化合物、具有(甲基)丙烯醯基之化合物的聚合物或共聚物、具有乙烯基之化合物、具有乙烯基之化合物的聚合物或共聚物、具有-C(=O)-O-基之化合物、具有-S-S-(disufide)基之化合物、具有三嗪環或三嗪三酮環之化合物、酚醛清漆、咔唑酚醛清漆、聚醯胺酸或聚醯亞胺。此處,(甲基)丙烯醯基,係指丙烯醯基或甲基丙烯醯基之意。
前述含選自由硼、鋁、鎵、碳、矽、鍺、氮、磷、砷、氧、硫及硒所構成之群中之至少1種之化合物,可例示如具有下述式(1)至式(24)所表示之構造單位或部分構造之聚合物或寡聚物。當含有前述至少1種之化合物為聚合物或寡聚物時,其之重量平均分子量,例如為1000至100000。又,重量平均分子量,係藉由凝膠滲透層析(GPC),使用聚苯乙烯作為標準試樣所得之值。
含有前述至少1種之化合物的含有比例,相對於前述離子注入用膜形成組成物整體,例如為30質量%至95質量%。
前述離子注入用膜形成組成物,可進一步含有交聯劑。該交聯劑,較佳為使用至少具有2個交聯形成取代基之交聯性化合物。可舉例如,具有羥甲基、甲氧基甲基等
之交聯形成取代基之三聚氰胺系化合物、及取代脲系化合物。具體而言,為甲氧基甲基化乙炔脲、甲氧基甲基化三聚氰胺等之化合物,可舉例如四甲氧基甲基乙炔脲、四丁氧基甲基乙炔脲、六甲氧基甲基三聚氰胺。再者,亦可舉例如四甲氧基甲基脲、四丁氧基甲基脲等之化合物。
前述交聯劑,又,亦可使用至少具有2個環氧基之化合物。如此之化合物,可舉例如,三(2,3-環氧基丙基)異氰酸酯、1,4-丁二醇二環氧丙醚、1,2-環氧基-4-(環氧基乙基)環己烷、甘油三環氧丙醚、二乙二醇二環氧丙醚、2,6-二環氧丙基苯基環氧丙醚、1,1,3-三[對(2,3-環氧基丙氧基)苯基]丙烷、1,2-環己烷二羧酸二環氧丙酯、4,4’-亞甲基雙(N,N-二環氧丙基苯胺)、3,4-環氧基環己基甲基-3,4-環氧基環己烷羧酸酯、三羥甲基乙烷三環氧丙醚、雙酚A-環氧丙醚、(股)Daicel製Epoled(註冊商標)GT-401、同GT-403、同GT-301、同GT-302、Celloxide(註冊商標)2021、同3000、三菱化學(股)製之1001、1002、1003、1004、1007、1009、1010、828、807、152、154、180S75、871、872、日本化藥(股)製之EPPN201、同202、EOCN-102、同103S、同104S、同1020、同1025、同1027、長瀨產業(股)製之Denacol(註冊商標)EX-252、同EX-611、同EX-612、同EX-614、同EX-622、同EX-411、同EX-512、同EX-522、同EX-421、同EX-313、同EX-314、同EX-321、BASF日本(股)製之CY175、CY177、CY179、CY182、CY184、CY192、
DIC(股)製之Epiclon200、同400、同7015、同835LV、同850CRP。
前述至少具有2個環氧基之化合物,亦可使用具有環氧基之聚合物。前述聚合物,只要為具有環氧基之聚合物即可使用,並無特別限制。如此之聚合物,可藉由使用具有環氧基之加成聚合性單體的加成聚合來製造,或者,藉由具有羥基之高分子化合物、與環氧氯丙烷、甲苯磺酸環氧丙酯等具有環氧基之化合物的反應來製造。例如,聚丙烯酸環氧丙酯、甲基丙烯酸環氧丙酯及甲基丙烯酸乙酯之共聚物、甲基丙烯酸環氧丙酯與苯乙烯與甲基丙烯酸2-羥基乙酯之共聚物等之加成聚合聚合物、環氧酚醛清漆等之縮聚合聚合物。前述聚合物之重量平均分子量,例如為300至200000。又,重量平均分子量,係藉由凝膠滲透層析(GPC),使用聚苯乙烯作為標準試樣所得之值。
前述至少具有2個環氧基之化合物,又,亦可使用具有胺基之環氧樹脂。如此之環氧樹脂,可舉例如YH-434、YH-434L(新日化環氧製造(股)(舊東都化成(股))製)。
前述交聯劑,又,亦可使用至少具有2個嵌段異氰酸酯基之化合物。如此之化合物,可舉例如,三井化學(股)製之Takenate(註冊商標)B-830、同B-870N、Evonik公司製之VESTANAT(註冊商標)-B1358/100。
前述交聯劑,又,亦可使用至少具有2個乙烯醚基之化合物。如此之化合物,可舉例如,雙(4-(乙烯氧基甲
基)環己基甲基)戊二酸酯、三(乙二醇)二乙烯醚、己二酸二乙烯酯、二乙二醇二乙烯醚、1,2,4-三(4-乙烯氧基丁基)偏苯三酸酯、1,3,5-三(4-乙烯氧基丁基)偏苯三酸酯、雙(4-(乙烯氧基)丁基)對苯二甲酸酯、雙(4-(乙烯氧基)丁基)間苯二甲酸酯、乙二醇二乙烯醚、1,4-丁二醇二乙烯醚、四亞甲基二醇二乙烯醚、四乙二醇二乙烯醚、新戊二醇二乙烯醚、三羥甲基丙烷三乙烯醚、三羥甲基乙烷三乙烯醚、己二醇二乙烯醚、1,4-環己二醇二乙烯醚、四乙二醇二乙烯醚、新戊四醇二乙烯醚、新戊四醇三乙烯醚及環己烷二甲醇二乙烯醚。
前述交聯劑,再者,亦可使用下述式(0)所表示之至少具有2個硼酸酯基之化合物(硼酸酯或硼酸酯)。
(式中,R表示碳原子數1~20之烷基、矽基、碳原子數1~20之鹵烷基、或可以碳原子數1~6之烷基、碳原子數1~6之鹵烷基及鹵素基之至少1種取代之苯基、萘基或蒽基,X表示亦可以鹵素基取代之碳原子數1~20之烷基、乙烯基、烯丙基、羥基、羧基、胺基、碳原子數1~20之烷硫基、氰基、乙醯基、乙醯氧基、碳原子數2~20之烷氧羰基、硝基、亞硝基、醯胺基、亞醯胺基、
碳原子數1~20之烷氧磺醯基、磺醯胺基、或可以碳原子數1~6之烷基、碳原子數1~6之鹵烷基及鹵素基之至少1種取代之苯基、萘基、蒽基或芘基,p表示2或3)。
如此之化合物,可舉例如,硼酸三甲酯、硼酸三乙酯、硼酸三丙酯、硼酸三異丙酯、硼酸三丁酯、硼酸三己酯、硼酸三-正辛酯、硼酸三癸酯、硼酸三-十四酯、硼酸三-十六酯、硼酸三-十八酯、硼酸三苯酯、硼酸三-鄰甲苯酯、硼酸三(4-氯苯基)酯、硼酸三(六氟異丙基)酯、三(三甲基矽基)硼酸酯、乙烯硼酸二丁酯、(溴甲基)硼酸二異丙酯、烯丙基硼酸二異丙酯。
於前述離子注入用膜形成組成物,可由該等之各種交聯劑選擇1種添加、亦可組合2種以上添加。於前述交聯劑所使用之化合物,亦可含有選自由前述之硼、鋁、鎵、碳、矽、鍺、氮、磷、砷、氧、硫及硒所構成之群中之至少一種元素。
前述交聯劑之含有比例,相對於由前述離子注入用膜形成組成物除去後述之有機溶劑的固體成分,例如為2質量%至60質量%。
前述離子注入用膜形成組成物,除前述交聯劑之外,可再含有交聯觸媒。前述交聯觸媒,可舉例如對甲苯磺酸、三氟甲烷磺酸、吡啶鎓-對甲苯磺酸、水楊酸、樟腦磺酸、5-磺柳酸、4-氯苯磺酸、4-羥基苯磺酸、苯二磺酸、1-萘磺酸、檸檬酸、苯甲酸、羥基苯甲酸等磺酸化合物及羧酸化合物、鹽酸、硫酸、硝酸、磷酸等之無機酸。
於前述離子注入用膜形成組成物,可由該等交聯劑之中選擇1種添加、亦可組合2種以上添加。前述交聯觸媒所使用之化合物,亦可含有選自由前述之硼、鋁、鎵、碳、矽、鍺、氮、磷、砷、氧、硫及硒所構成之群中之至少一種元素。
前述交聯觸媒之含有比例,相對於由前述離子注入用膜形成組成物除去後述之有機溶劑的固體成分,例如為0.1質量%至10質量%。
前述離子注入用膜形成組成物,亦可進一步含有界面活性劑。前述界面活性劑,可舉例如,聚氧乙烯月桂醚、聚氧乙烯硬酯醚、聚氧乙烯十六醚、聚氧乙烯油醚等聚氧乙烯烷基醚類、聚氧乙烯辛基苯酚醚、聚氧乙烯壬基苯酚醚等聚氧乙烯烷基芳基醚類、聚氧乙烯‧聚氧丙烯嵌段共聚物類、山梨醇酐單月桂酸酯、山梨醇酐單軟脂酸酯、山梨醇酐單硬脂酸酯、山梨醇酐單油酸酯、山梨醇酐三油酸酯、山梨醇酐三硬脂酸酯等山梨醇酐脂肪酸酯類、聚氧乙烯山梨醇酐單月桂酸酯、聚氧乙烯山梨醇酐單軟脂酸酯、聚氧乙烯山梨醇酐單硬脂酸酯、聚氧乙烯山梨醇酐三油酸酯、聚氧乙烯山梨醇酐三硬脂酸酯等聚氧乙烯山梨醇酐脂肪酸酯類等之非離子系界面活性劑、Ftop(註冊商標)EF301、同EF303、同EF352(三菱材料電子化成(股)(舊股份有限公司JEMCO)製)、MEGAFACE(註冊商標)F171、同F173、同R30、同R-30-N(DIC股份有限公司製)、Fluorad FC430、FC431(住友3M(股)製)、
AsahiGuard(註冊商標)AG710、SURFLON(註冊商標)S-382、同SC101、同SC102、同SC103、同SC104、同SC105、同SC106(旭硝子(股)製)等氟系界面活性劑、有機聚矽氧烷聚合物KP341(信越化學工業(股))。前述離子注入用膜形成組成物,可由該等之界面活性劑選擇1種添加、亦可組合2種以上添加。
前述界面活性劑之含有比例,相對於由前述離子注入用膜形成組成物除去後述之有機溶劑的固體成分,例如為0.01質量%至5質量%。
前述離子注入用膜形成組成物,可進一步含有苯酚衍生物。苯酚衍生物,可使垂直於基板方向之光阻圖型截面抑制為基腳形狀,為有助於成為所欲之形狀(矩形)的添加物。苯酚衍生物之具體例,可舉例如,4-甲基磺醯基苯酚、雙酚S、雙酚AF、4-氰基苯酚、3,4,5-三氟苯酚、4-羥基三氟甲苯、2,3,5,6-四氟-4-(三氟甲基)苯酚、2,6-二氯-4-(甲基磺醯基)苯酚。
前述苯酚衍生物之含有比例,相對於由前述離子注入用膜形成組成物除去後述之有機溶劑的固體成分,例如為0.1質量%至20質量%。
前述離子注入用膜形成組成物,藉由使前述各成分溶解於適當之有機溶劑可調製,而能以均勻的溶液狀態使用。如此之有機溶劑,可舉例如,乙二醇單甲醚、乙二醇單乙醚、二乙二醇單甲醚、二乙二醇單乙醚、丙二醇、丙二醇單甲醚、丙二醇單丙醚、丙二醇單甲醚乙酸酯、丙二
醇丙醚乙酸酯、甲賽璐蘇乙酸酯、乙賽璐蘇乙酸酯、甲苯、二甲苯、甲乙酮、環戊酮、環己酮、2-羥基丙酸乙酯、2-羥基-3-甲基丙酸甲酯、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、乙酸乙酯、乙酸丁酯、乳酸乙酯、乳酸丁酯、N,N-二甲基甲醯胺、N,N-二乙基甲醯胺、N-甲基吡咯烷酮。該等有機溶液,可使用1種或組合2種以上使用。
由前述離子注入用膜形成組成物除去有機溶劑之固體成分的比例,例如為0.5質量%至30質量%、較佳為0.8質量%至10質量%。
前述離子注入用膜形成組成物所含之含有選自由前述之硼、鋁、鎵、碳、矽、鍺、氮、磷、砷、氧、硫及硒所構成之群中之至少一種之化合物、及任意成分,亦為本發明之光阻下層膜形成組成物的成分,可藉由溶解於前述有機溶劑來調製。本發明之光阻下層膜形成組成物係含有前述式(0)所表示之化合物,例如硼酸三甲酯、硼酸三乙酯、硼酸三丙酯、硼酸三異丙酯、硼酸三丁酯、硼酸三己酯、硼酸三-正辛酯、硼酸三癸酯、硼酸三-十四酯、硼酸三-十六酯、硼酸三-十八酯、硼酸三苯酯、硼酸三-鄰甲苯酯、硼酸三(4-氯苯基)酯、硼酸三(六氟異丙基)酯、三(三甲基矽基)硼酸酯、乙烯硼酸二丁酯、(溴甲基)硼酸二異丙酯或烯丙基硼酸二異丙酯作為必須成分。
式(0)所表示之化合物之含有比例,相對於由前述
光阻下層膜形成組成物除去前述之有機溶劑的固體成分,例如為10質量%至40質量%。
本發明之光阻下層膜形成組成物,亦可進一步含有具(甲基)丙烯醯基之化合物、具(甲基)丙烯醯基之化合物的聚合物或共聚物、具有乙烯基之化合物、具有乙烯基之化合物的聚合物或共聚物、具有-C(=O)-O-基之化合物、具有-S-S-(disufide)基之化合物、具有三嗪環或三嗪三酮環之化合物、酚醛清漆、咔唑酚醛清漆、聚醯胺酸或聚醯亞胺,亦可含有具有前述式(1)至式(24)所表示之構造單位或部分構造之聚合物或共聚物。
以下,舉合成例及實施例以說明本發明,但本發明並不限於下述記載。
下述合成例1至合成例7所示之重量平均分子量,係根據凝膠滲透層析(以下,於本說明書簡稱為GPC)之測定結果。測定時,係使用東索(股)製GPC裝置,測定條件係如下述所示。
GPC管柱:Shodex[註冊商標]‧Asahipak[註冊商標](昭和電工(股)製)
管柱溫度:40℃
溶劑:N,N-二甲基甲醯胺(DMF)
流量:0.6mL/分鐘
標準試樣:聚苯乙烯(東索(股)製)
使甲基丙烯酸環氧丙酯21.0g與甲基丙烯酸2-羥基丙酯39.5g溶解於丙二醇單甲醚244.6g後,加熱於保持為70℃下,添加偶氮雙異丁腈0.6g,使其反應24小時製得甲基丙烯酸環氧丙酯與甲基丙烯酸2-羥基丙酯之共聚合高分子化合物的溶液。進行所得之共聚合高分子化合物之GPC分析的結果,以標準苯乙烯換算之重量平均分子量為約50000。於含有該共聚合高分子化合物20g之溶液100g,添加9-蒽羧酸10g、苄基三乙基銨氯化物0.3g及丙二醇單甲醚41g,加熱後以120℃反應24小時,製得具有以下述式(A-1)所表示之構造單位之高分子化合物的溶液。
使下述式(A-2)所表示之三嗪化合物10.0g與下述式(A-3)所表示之苯胍化合物10.0g溶解於乳酸乙酯
100g後,添加對甲苯磺酸0.5g,於加熱後保持於120℃反應24小時,製得具有以下述式(A-4)所表示之構造單位之高分子化合物的溶液。進行所得之高分子化合物之GPC分析的結果,以標準苯乙烯換算之重量平均分子量為約12000。
[式(A-4)中,各X表示以“-CH2OCH2-”或“-CH2-”所表示之連結基]。
使單烯丙基二環氧丙基異三聚氰酸(四國化成工業(股)製)5.0g、3,3’-二硫二丙酸(堺化學工業(股)製,商
品名:DTDPA)3.8g、及觸媒之四級鏻鹽之三苯基單乙基鏻溴化物0.3g,溶解於丙二醇單甲醚13.8g,加熱後保持於120℃於氮環境氣氛下攪拌4小時。將所得之反應生成物,進行以丙二醇單甲醚23.0g稀釋之清漆溶液之GPC分析的結果,以標準聚苯乙烯換算之重量平均分子量為約7800。該反應生成物,含有具下述式(A-5)所表示之構造單位之高分子化合物。
使單烯丙基二環氧丙基異三聚氰酸(四國化成工業(股)製)10.00g、乙二硫醇(四國化成工業(股)製)4.98g、及觸媒之四級鏻鹽之苄基三乙基銨氯化物0.40g,溶解於丙二醇單甲醚61.52g,加熱後保持於120℃反應24小時。進行含有所得之反應生成物之清漆溶液之GPC分析的結果,以標準聚苯乙烯換算之重量平均分子量為約16800。該反應生成物,含有具下述式(A-6)所表示之構造單位之高分子化合物。
將三-(2,3-環氧基丙基)-異三聚氰酸酯10.0g添加至二甲苯24.0g使其溶解。於該溶解液,添加苯酚3.2g與苄基三乙基銨氯化物0.57g,加熱後保持於140℃反應24小時。反應後放置冷卻,將可析出之聚合物過濾後,以二甲苯洗淨,之後乾燥。將所得之聚合物化合物之構造示於下述示(A-7)。該聚合物之重量平均分子量為約3000。
使2,6-萘二羧酸7.0g溶解於N-甲基吡咯烷酮67g後,添加1,2-環己烷二羧酸二環氧丙酯9.2g與苄基三乙基銨氯化物0.6g,加熱後保持於130℃反應24小時製得
下述式(A-8)之高分子化合物的溶液。進行所得之高分子化合物之GPC分析的結果,以標準聚苯乙烯換算之重量平均分子量為約6000。
將咔唑(東京化成工業(股)製)8g、1-萘醛(東京化成工業(股)製)7.55g、對甲苯磺酸一水合物(關東化學(股)製)0.95g及1,4-二噁烷(關東化學(股)製)8g混合,加熱後保持於100℃於氮環境氣氛下攪拌4小時。之後放置冷卻至60℃後,加入氯仿40g以稀釋,於甲醇200g使其再沉澱。將所得之沉澱物過濾,以減壓乾燥機以60℃乾燥10小時、再以120℃乾燥24小時,製得目的之含有具有下述式(A-9)所表示之構造單位的高分子化合物10.03g。進行所得之高分子化合物之GPC分析的結果,以標準聚苯乙烯換算之重量平均分子量為約2600。
於含有前述合成例1所得之高分子化合物2g之溶液10g,加入六甲氧基甲基三聚氰胺[Cymel(註冊商標)303、日本氰特工業(股)製]0.26g、對甲苯磺酸0.01g、丙二醇單甲醚37.2g及丙二醇單甲醚乙酸酯19.4g作成溶液。之後,使用孔徑0.10μm之聚乙烯製微過濾器進行過濾,再使用孔徑0.02μm之聚乙烯製微過濾器進行過濾,調製成離子注入用膜形成組成物。
於含有前述合成例1所得之高分子化合物2g之溶液10g,加入硼酸三丁酯(東京化成工業(股)製)0.60g、丙二醇單甲醚35.7g及丙二醇單甲醚乙酸酯18.7g作成溶液。之後,使用孔徑0.10μm之聚乙烯製微過濾器進行過濾,再使用孔徑0.02μm之聚乙烯製微過濾器進行過濾,調製成離子注入用膜形成組成物。
於含有前述合成例1所得之高分子化合物2g之溶液10g,加入六甲氧基甲基三聚氰胺[Cymel(註冊商標)303、日本氰特工業(股)製]0.27g、對甲苯磺酸0.01g、85%磷酸水溶液0.4g(關東化學(股)製)、丙二醇單甲醚36.9g及丙二醇單甲醚乙酸酯19.3g作成溶液。之後,使
用孔徑0.10μm之聚乙烯製微過濾器進行過濾,再使用孔徑0.02μm之聚乙烯製微過濾器進行過濾,調製成離子注入用膜形成組成物。
於含有前述合成例1所得之高分子化合物2g之溶液10g,加入四甲氧基甲基乙炔脲[POWDERLINK(註冊商標)1174、日本氰特工業(股)製]0.5g、對甲苯磺酸0.02g、85%磷酸水溶液0.44g(關東化學(股)製)、丙二醇單甲醚41.69g及丙二醇單甲醚乙酸酯21.30g作成溶液。之後,使用孔徑0.10μm之聚乙烯製微過濾器進行過濾,再使用孔徑0.02μm之聚乙烯製微過濾器進行過濾,調製成離子注入用膜形成組成物。
於含有前述合成例2所得之高分子化合物2g之溶液10g,加入對甲苯磺酸0.05g、吡啶鎓-對甲苯磺酸酯0.11g、乳酸乙酯17.9g及丙二醇單甲醚乙酸酯25.9g作成溶液。之後,使用孔徑0.10μm之聚乙烯製微過濾器進行過濾,再使用孔徑0.02μm之聚乙烯製微過濾器進行過濾,調製成離子注入用膜形成組成物。
於含有前述合成例3所得之高分子化合物2g之溶液
10g,加入四甲氧基甲基乙炔脲[POWDERLINK(註冊商標)1174、日本氰特工業(股)製]0.5g、4-羥基苯磺酸(PSA)0.05g、雙酚S0.03g、介面活性劑(R-30、DIC(股))0.004g、丙二醇單甲醚35.4g及丙二醇單甲醚乙酸酯18.6g作成溶液。之後,使用孔徑0.10μm之聚乙烯製微過濾器進行過濾,再使用孔徑0.02μm之聚乙烯製微過濾器進行過濾,調製成離子注入用膜形成組成物。
於含有前述合成例7所得之高分子化合物2g之溶液10g,加入四甲氧基甲基乙炔脲[POWDERLINK(註冊商標)1174、日本氰特工業(股)製]0.3g、吡啶鎓-對甲苯磺酸酯0.03g、界面活性劑(R-30、DIC(股))0.01g、丙二醇單甲醚25.6g、環己酮11.2g及丙二醇單甲醚11.2g作成溶液。之後,使用孔徑0.10μm之聚乙烯製微過濾器進行過濾,再使用孔徑0.02μm之聚乙烯製微過濾器進行過濾,調製成離子注入用膜形成組成物。
計算實施例1至實施例7所調製之離子注入用膜形成組成物之固體成分中所含之各元素的含有率(個數%)。此時所使用之計算方法係示於以下。
1.計算相對於離子注入用膜形成組成物中之固體成分的高分子化合物、交聯劑及交聯觸媒之質量比。
2.使用分子量(為高分子化合物時使用構造單位或部分構造中之分子量),計算相對於離子注入用膜形成組成物中之固體成分的高分子化合物、交聯劑及交聯觸媒之莫耳比。
3.使用高分子化合物、交聯劑及交聯觸媒所含之各元素的個數及莫耳比,計算離子注入用膜形成組成物中之固體成分所含之總元素及各元素之數,使用下述式求出各元素之含有率(個數%)。
[(離子注入用膜形成組成物中之固體成分所含之各元素的總數)/(離子注入用膜形成組成物中之固體成分所含之總元素數)]×100
將結果式於下述表1。
將實施例1至實施例7所調製之離子注入用膜形成組成物,使用旋轉器塗佈於基板(矽晶圓)上之後,使用加
熱板,以205℃烘烤1分鐘,形成膜(膜厚0.05μm)。
於使用實施例1至實施例7所調製之離子注入用膜形成組成物形成膜的基板,使用日新離子機器(股)製離子注入裝置EXCEED3000AH,以80keV、6.5×1015cm2之條件由前述膜的上方離子注入硼。
於使用實施例1至實施例7所調製之離子注入用膜形成組成物形成膜的基板,使用日新離子機器(股)製離子注入裝置EXCEED3000AH,以80keV、6.5×1015cm2之條件由前述膜的上方離子注入氬。
於未形成膜之基板(矽晶圓)單體,進行前述離子注入A,製作離子注入基板。
於未形成膜之基板(矽晶圓)單體,進行前述離子注入B,製作離子注入基板。
對於離子注入後之基板,使用日本Scientific(股)製
RIE系統ES401,以使用O2作為乾式蝕刻氣體的條件,除去膜。接著,以HF水溶液進行處理,藉此除去基板表面之氧化矽膜後,使用CAMECA公司製IMS-6f及PHI公司製Model6300測定基板之深度方向中之元素濃度分布。將以離子注入A所得之結果示於圖1至圖5,以離子注入B所得之結果示於圖6至圖8。
以離子注入A所得之圖1至圖4中,圖1,係由使用含碳之實施例1及實施例7之離子注入用膜形成組成物所形成之膜的上方進行離子注入的情形,相對於比較例1,顯示基板內之碳濃度為大的結果。圖2,係由使用含氮之實施例5之離子注入用膜形成組成物所形成之膜的上方進行離子注入的情形,相對於比較例1,顯示基板內之氮濃度為大的結果。圖3,係由使用含磷之實施例3之離子注入用膜形成組成物所形成之膜的上方進行離子注入的情形,相對於比較例1,顯示基板內之磷濃度為大的結果。
圖4,係由使用含硫之實施例6之離子注入用膜形成組成物所形成之膜的上方進行離子注入的情形,相對於比較例1,顯示基板內之硫濃度為大的結果。由圖1至圖4所示之結果可知,於離子注入步驟中,可將前述膜中之元素導入基板內。圖5,係顯示由使用實施例1之離子注入用膜形成組成物所形成之膜的上方離子注入硼,藉此,硼與前述膜中之元素一同被導入基板內。
以離子注入B所得之圖6至圖8中,圖6,係顯示由使用含碳之實施例4之離子注入用膜形成組成物所形成之
膜的上方進行離子注入的情形,相對於比較例2,顯示基板內之碳濃度為大的結果。圖7,係顯示由使用含磷之實施例4之離子注入用膜形成組成物所形成之膜的上方進行離子注入的情形,相對於比較例2,顯示基板內之磷濃度為大的結果。圖8,係顯示由使用含硼之實施例2之離子注入用膜形成組成物所形成之膜的上方進行離子注入的情形,相對於比較例2,顯示基板內之硼濃度為大的結果。由圖6至圖8所示之結果可知,即使改變由膜之上方所注入之離子種,亦可將膜中所含之元素導入基板內。
於含有前述合成例1所得之高分子化合物2g之溶液10g,加入硼酸三丁酯(東京化成工業(股)製)0.60g、R-30N(DIC(股)製)0.01g、丙二醇單甲醚35.8g及丙二醇單甲醚乙酸酯18.7g作成溶液。之後,使用孔徑0.10μm之聚乙烯製微過濾器進行過濾,再使用孔徑0.02μm之聚乙烯製微過濾器進行過濾,調製成光阻下層膜形成組成物。
於含有前述合成例1所得之高分子化合物2g,之溶液10g,加入四甲氧基甲基乙炔脲[POWDERLINK(註冊商標)1174、日本氰特工業(股)製]0.48g、對甲苯磺酸0.01g、丙二醇單甲醚34.0g及丙二醇單甲醚18.0g作成溶液。之後,使用孔徑0.10μm之聚乙烯製微過濾器進行過
濾,再使用孔徑0.02μm之聚乙烯製微過濾器進行過濾,調製成光阻下層膜形成組成物。
將以實施例8及比較例3所調製之光阻下層膜形成組成物,分別以旋轉器塗佈於矽晶圓上。於加熱板上,以205℃加熱1分鐘,形成光阻下層膜。將該光阻下層膜浸漬於光阻塗佈時所使用之溶劑之OK73油漆稀釋劑(東京應化工業(股)製,丙二醇單甲醚及丙二醇單甲醚乙酸酯之混合溶劑)1分鐘,確認浸漬前後之光阻下層膜之膜厚變化為1nm以下。
將以實施例8及比較例3所調製之光阻下層膜形成組成物,分別以旋轉器塗佈於矽晶圓上。於加熱板上,以205℃加熱1分鐘,形成光阻下層膜(膜厚0.05μm)。接著,將該等之光阻下層膜使用分光橢圓偏振計(J.A.Woollam公司製、VUV-VASE VU-302),測定以波長248nm之折射率(n值)及衰減係數(k值)。將其之結果示於表2。同樣的,將以波長193nm之折射率(n值)及衰減係數(k值)的測定結果示於表3。由表2及表3之結果顯示,以實施例8及比較例3所調製之光阻下層膜形成組成物作為光阻下層膜,具有曝光時對光阻之抗反射的特性。
將以實施例8及比較例3所調製之光阻下層膜形成組成物,分別以旋轉器塗佈於矽晶圓上。於加熱板上,以205℃加熱1分鐘,形成光阻下層膜。於該等光阻下層膜上,以旋轉器塗佈光阻TDUR-P3435LP(東京應化工業(股)製)。於加熱板上,以90℃加熱1分鐘,使用(股)尼康製掃描器S-205C(波長248nm,NA:0.75,σ:0.85(慣用(Conventional)照明)),透過後述之光罩以既定之曝光量曝光。接著,使用加熱板,以110℃實施曝光後加熱(Post Exposure Bake)1分鐘。冷卻後,使用作為顯像液之2.38質量%之四甲基氫氧化銨水溶液顯像60秒鐘。
將矽晶圓表面以1,1,1,3,3,3-六甲基二矽氮烷(HMDS)以90℃處理1分鐘,於該矽晶圓表面上,以旋轉器塗佈光阻TDUR-P3435LP(東京應化工業(股)製)。於加熱板上,以90℃加熱1分鐘,使用(股)尼康製掃描器S-205C(波長248nm,NA:0.75,σ:0.85(慣用(Conventional)照明)),透過後述之光罩以既定之曝光量曝光。接著,使用加熱板,以110℃實施曝光後加熱(Post Exposure Bake)1分鐘。冷卻後,使用作為顯像液之2.38質量%之四甲基氫氧化銨水溶液顯像60秒鐘。
於前述形成步驟及比較例4中,係使用描繪有交互重覆之200nm線寬與200nm線距之圖型的光罩進行曝光,所得之光阻之圖型,確認形成為光罩之線寬之尺寸的曝光量。測定係使用(股)日立高科技製CD-SEM之S-9380進行。將結果示於表4。
將以表4所示之曝光量所製作之光阻圖型,以(股)日
立高科技製之掃描型電子顯微鏡(SEM)S-4800觀察與基板(矽晶圓)垂直方向之截面。其之結果,所得之光阻圖型之截面形狀,皆為良好之直線之邊形狀,大致皆觀察到矩形。使用實施例8及比較例3之光阻下層膜形成組成物,將對前述方法所得之光阻圖型之截面攝影之SEM影像,分別示於圖9及圖10。再者,將對以比較例4所記載之步驟所得之光阻圖型之截面攝影之SEM影像,示於圖11。由表4及圖9,顯示實施例8之光阻下層膜形成組成物,可於不使光阻形狀惡化之下,使光阻感度大幅地增加。
Claims (8)
- 一種離子注入方法,包含:將含有含13族、14族、15族或16族之元素的化合物及有機溶劑的膜形成組成物,塗佈於基板上烘烤而形成膜;及將雜質離子由前述膜之上方介由前述膜而注入前述基板,且同時將前述膜中之13族、14族、15族或16族之元素導入前述基板中。
- 如申請專利範圍第1項之離子注入方法,進一步包含:於前述形成膜之後、將前述雜質離子注入前述基板之前,於該膜上形成光阻圖型,其中於該膜上形成光阻圖型包括將光阻溶液塗佈於該膜烘烤而形成光阻膜,對於形成光阻膜之基板,透過該光罩進行曝光,並接著以鹼性顯像液或有機溶劑進行顯像以形成光阻圖型。
- 如申請專利範圍第1項之離子注入方法,其中,該雜質離子之離子種為硼、磷、砷、碳、氮、氧、氟、氬、矽、鎵、鍺、銦或銻。
- 如申請專利範圍第1項之離子注入方法,其中,該含13族、14族、15族或16族之元素的化合物係含有選自由硼、鋁、鎵、碳、矽、鍺、氮、磷、砷、氧、硫及硒所構成之群中之至少一種的化合物。
- 一種離子注入用膜形成組成物,其係含有具有式(1)至式(24)所表示之構造單位或部分構造之聚合物 或寡聚物及有機溶劑的離子注入用膜形成組成物,其特徵係,該具有式(1)至式(24)所表示之構造單位或部分構造之聚合物或寡聚物係含有選自由硼、鋁、鎵、碳、矽、鍺、氮、磷、砷、氧、硫及硒所構成之群中之至少一種的化合物,
- 如申請專利範圍第5項之離子注入用膜形成組成 物,其係進一步含有交聯劑。
- 如申請專利範圍第6項之離子注入用膜形成組成物,其係進一步含有交聯觸媒。
- 如申請專利範圍第5項之離子注入用膜形成組成物,其係進一步含有界面活性劑。
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KR101880201B1 (ko) | 2018-07-20 |
KR20180082617A (ko) | 2018-07-18 |
JP6168324B2 (ja) | 2017-07-26 |
TW201716874A (zh) | 2017-05-16 |
JPWO2013118879A1 (ja) | 2015-05-11 |
KR20190039354A (ko) | 2019-04-10 |
TW201346451A (zh) | 2013-11-16 |
JP6075586B2 (ja) | 2017-02-08 |
US9214345B2 (en) | 2015-12-15 |
JP6037137B2 (ja) | 2016-11-30 |
KR101926739B1 (ko) | 2018-12-07 |
CN104094381B (zh) | 2016-12-28 |
KR20180081831A (ko) | 2018-07-17 |
US20150017791A1 (en) | 2015-01-15 |
JP2016146486A (ja) | 2016-08-12 |
JP2016128925A (ja) | 2016-07-14 |
CN104094381A (zh) | 2014-10-08 |
WO2013118879A1 (ja) | 2013-08-15 |
KR102072499B1 (ko) | 2020-02-03 |
TWI602027B (zh) | 2017-10-11 |
KR20140133834A (ko) | 2014-11-20 |
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