WO2002080233A2 - Process and apparatus for removing residues from the microstructure of an object - Google Patents
Process and apparatus for removing residues from the microstructure of an object Download PDFInfo
- Publication number
- WO2002080233A2 WO2002080233A2 PCT/US2002/003608 US0203608W WO02080233A2 WO 2002080233 A2 WO2002080233 A2 WO 2002080233A2 US 0203608 W US0203608 W US 0203608W WO 02080233 A2 WO02080233 A2 WO 02080233A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- vessel
- additive
- residues
- solvent
- process according
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 30
- 239000000654 additive Substances 0.000 claims abstract description 62
- 230000000996 additive effect Effects 0.000 claims abstract description 52
- 239000006184 cosolvent Substances 0.000 claims abstract description 39
- 239000012530 fluid Substances 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 38
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 20
- 239000004065 semiconductor Substances 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- MOVBJUGHBJJKOW-UHFFFAOYSA-N methyl 2-amino-5-methoxybenzoate Chemical compound COC(=O)C1=CC(OC)=CC=C1N MOVBJUGHBJJKOW-UHFFFAOYSA-N 0.000 claims description 6
- 150000003973 alkyl amines Chemical class 0.000 claims description 5
- 150000007514 bases Chemical class 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 3
- 125000003158 alcohol group Chemical group 0.000 claims 2
- 238000010438 heat treatment Methods 0.000 claims 2
- 238000004380 ashing Methods 0.000 claims 1
- 238000005530 etching Methods 0.000 claims 1
- 235000012431 wafers Nutrition 0.000 description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 11
- 229910052710 silicon Inorganic materials 0.000 description 11
- 239000010703 silicon Substances 0.000 description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 5
- GTDKXDWWMOMSFL-UHFFFAOYSA-M tetramethylazanium;fluoride Chemical compound [F-].C[N+](C)(C)C GTDKXDWWMOMSFL-UHFFFAOYSA-M 0.000 description 5
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 4
- 229960001231 choline Drugs 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- -1 TMAF Chemical compound 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 3
- QSUJAUYJBJRLKV-UHFFFAOYSA-M tetraethylazanium;fluoride Chemical compound [F-].CC[N+](CC)(CC)CC QSUJAUYJBJRLKV-UHFFFAOYSA-M 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 229960004592 isopropanol Drugs 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 1
- FHCUSSBEGLCCHQ-UHFFFAOYSA-M 2-hydroxyethyl(trimethyl)azanium;fluoride Chemical compound [F-].C[N+](C)(C)CCO FHCUSSBEGLCCHQ-UHFFFAOYSA-M 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- SDIXRDNYIMOKSG-UHFFFAOYSA-L disodium methyl arsenate Chemical compound [Na+].[Na+].C[As]([O-])([O-])=O SDIXRDNYIMOKSG-UHFFFAOYSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- PRERWTIRVMYUMG-UHFFFAOYSA-N hydroxymethyl(trimethyl)azanium Chemical compound C[N+](C)(C)CO PRERWTIRVMYUMG-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- CKFGINPQOCXMAZ-UHFFFAOYSA-N methanediol Chemical compound OCO CKFGINPQOCXMAZ-UHFFFAOYSA-N 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229960004063 propylene glycol Drugs 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 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
- POSYVRHKTFDJTR-UHFFFAOYSA-M tetrapropylazanium;fluoride Chemical compound [F-].CCC[N+](CCC)(CCC)CCC POSYVRHKTFDJTR-UHFFFAOYSA-M 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
-
- 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
- H01L21/3065—Plasma etching; Reactive-ion etching
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B7/00—Cleaning by methods not provided for in a single other subclass or a single group in this subclass
- B08B7/0021—Cleaning by methods not provided for in a single other subclass or a single group in this subclass by liquid gases or supercritical fluids
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/10—Salts
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
- C11D7/3209—Amines or imines with one to four nitrogen atoms; Quaternized amines
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
- C11D7/3218—Alkanolamines or alkanolimines
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/50—Solvents
- C11D7/5004—Organic solvents
-
- 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
- G03F7/42—Stripping or agents therefor
- G03F7/422—Stripping or agents therefor using liquids only
-
- 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
- G03F7/42—Stripping or agents therefor
- G03F7/422—Stripping or agents therefor using liquids only
- G03F7/425—Stripping or agents therefor using liquids only containing mineral alkaline compounds; containing organic basic compounds, e.g. quaternary ammonium compounds; containing heterocyclic basic compounds containing nitrogen
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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
- H01L21/311—Etching the insulating layers by chemical or physical means
- H01L21/31105—Etching inorganic layers
- H01L21/31111—Etching inorganic layers by chemical means
- H01L21/31116—Etching inorganic layers by chemical means by dry-etching
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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
- H01L21/311—Etching the insulating layers by chemical or physical means
- H01L21/31127—Etching organic layers
- H01L21/31133—Etching organic layers by chemical means
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/14—Hard surfaces
- C11D2111/22—Electronic devices, e.g. PCBs or semiconductors
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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
- H01L21/02043—Cleaning before device manufacture, i.e. Begin-Of-Line process
- H01L21/02052—Wet cleaning only
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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
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/67005—Apparatus not specifically provided for elsewhere
- H01L21/67011—Apparatus for manufacture or treatment
- H01L21/67017—Apparatus for fluid treatment
- H01L21/67063—Apparatus for fluid treatment for etching
- H01L21/67075—Apparatus for fluid treatment for etching for wet etching
- H01L21/67086—Apparatus for fluid treatment for etching for wet etching with the semiconductor substrates being dipped in baths or vessels
Definitions
- the present invention relates to a process and an apparatus for removing residues from the microstructure of an object.
- the present invention specifically relates to a process and an apparatus for removing residues, such as resists, generated during a semiconductor manufacturing process from a semiconductor wafer surface having a fine structure of convex and concave portions.
- residues such as photoresists, UV-hardened resists, X-ray hardened resists, ashed resists, carbon- fluorine containing polymer, plasma etch residues, and organic or inorganic contaminants from the other steps of the manufacturing process.
- the dry and wet removal methods are commonly used.
- the semiconductor wafer is dipped in an agent, such as a water solution, including a remover to remove residues from the surface of semiconductor wafer.
- an agent such as a water solution
- a remover to remove residues from the surface of semiconductor wafer.
- supercritical CO 2 is used as such an agent because of its low viscosity.
- An object of the present invention is, therefore, to provide a process and an apparatus for effectively removing residues from the microstructure of an object.
- a process for removing residues from the object comprises steps of preparing a remover including a CO 2 , an additive for removing the residues and a co-solvent for dissolving said additive in said CO 2 at a pressurized fluid condition, and bringing the object into contact with said remover so as to remove the residues from the object.
- a process is further provided for removing residues from the microstructure of an object, which comprises a step of contacting the object with a remover including a supercritical CO 2 , a compound having hydroxyl group, and a fluoride of formula NR1R2R3R4F, where R represents a hydrogen or alkyl group.
- An apparatus for removing residues from the object, which comprises a vessel, at least one inlet for feeding into said vessel a CO 2 , an additive for removing the residues and a co-solvent for dissolving said additive in said CO 2 , a pump for pressurizing CO 2 into said vessel, and a heater for keeping said pressurized CO 2 at a predetermined temperature.
- FIG. 1 is a schematic diagram of an apparatus for removing residues in accordance with the present invention.
- FIG. 2 is a schematic diagram of another embodiment of the apparatus for removing residues in accordance with the present invention.
- FIG. 3 shows an effect of the concentration of tetramethylammoniumfluoride (hereinafter referred to as "TMAF") on the etch rate.
- TMAF tetramethylammoniumfluoride
- FIG. 4 shows an effect of the concentration of ethanol on the etch rate.
- FIG. 5 is a schematic diagram of a third embodiment of the apparatus for removing residues in accordance with the present invention.
- the present invention is applied to the microstructure of an object, e.g., a semiconductor wafer having a fine structure of convex and concave portions on its surface, and a substrate made of a metal, plastic or ceramic which forms or remains continuous or non- continuous layer of materials different therefrom.
- an object e.g., a semiconductor wafer having a fine structure of convex and concave portions on its surface, and a substrate made of a metal, plastic or ceramic which forms or remains continuous or non- continuous layer of materials different therefrom.
- the pressurized CO 2 of the present invention As the pressurized CO 2 is not enough by itself to remove residues, the pressurized CO 2 of the present invention, to which an additive and a co-solvent are added, is used as a remover for removing residues from the object.
- the additive used for this purpose can remove residues but cannot substantially dissolve in CO 2 by itself.
- the co-solvent used for this purpose can make the additive dissolved or dispersed homogeneously in CO 2 .
- the pressurized CO 2 has a high dispersion rate and enables the dissolved residues to disperse therein. If CO2 is converted to a supercritical condition, it penetrates into fine pattern portions of the object more effectively. By this feature, the additive is conveyed into pores or concave portions on a surface of the object due to the low viscosity of CO 2 .
- the CO 2 is pressurized to 5 MPa or more, but not less than 7.1 MPa at a temperature of 31°C to convert the CO 2 to a supercritical fluid condition.
- the basic compound is preferably used as the additive because it effectively hydrolyzes polymers typically used as a resist in manufacturing a semiconductor.
- the preferred basic compound includes at least one element selected from the group consisting of quaternaryammoniumhydroxide, quaternaryammoniumfluoride, alkylamine, alkanolamine, hydroxylamine, and ammoniumfluoride. It is preferred to use a compound including at least one of quaternaryammoniumhydroxide, quate ⁇ aryammoniumfluoride, hydroxyammine and ammoniumfluoride to remove novolac phenol resists from a semiconductor wafer.
- the quaternaryammoniumhydroxide may be any quaternaryammoniumhydroxide, e.g.
- the quaternaryammoniumfluoride may be any quaternaryammoniumfluoride, e.g. tetramethylammoniumfluoride (hereinafter referred as TMAF), tetraethylammoniumfluoride, tetrapropylammoniumfluoride, tetrabutylammoniumfluoride, and cholinefluoride.
- TMAF tetramethylammoniumfluoride
- the alkylamine may be any alkylamine, e.g.
- the alkanolamine may be any alkanolamine, e.g., monoethanolamine, diethanolamine, and triethanolamine.
- the additive is preferably added in a ratio of not less than 0.001 wt. % of the remover, more preferably in a ratio of not less than 0.002 wt. %.
- the co-solvent should be added more, but the amount of CO 2 is decreased according to the amount of the added co-solvent, which decreases the penetration of CO2 into a surface of the object.
- the upper range of the additive is 8 wt. %, preferably 6 wt. %, and more preferably 4 wt. %.
- the co-solvent is added to CO 2 together with the additive.
- the co-solvent of the present invention is a compound having an affinity to both CO2 and the additive. Such a co-solvent dissolves or disperses the additive homogeneously in the pressurized CO 2 in fluid condition.
- An alcohol, dimethylsulfoxide or a mixture thereof is used as the co-solvent.
- the alcohol may be any alcohol, e.g.
- ethanol methanol, n-propanol, iso-propanol, n-butanol, iso-butanol, diethyleneglycolmonomethyleter, diethyleneglycolmonoethyleter, and hexafluoro isopropanol, preferably ethanol and methanol.
- the kind and amount of the co-solvent are selected depending on the kind and amount of the additive to CO 2 .
- the amount of the co-solvent is preferably five times or more than that of the additive because the remover easily becomes homogeneous and transparent.
- the remover may include the co-solvent in a range of 1 wt. % to 50 wt. %. If more than 50 wt. % of the co-solvent is added, the penetration rate of the remover decreases due to less amount of CO 2 .
- a remover including CO 2 , alcohol as the co-solvent, quaternaryammoniumfluoride and/or quaternaryammoniumhydroxide as the additive because these additives are well dissolved in CO 2 by alcohol and are C ⁇ 2 -philic.
- a remover composed of CO 2 , a fluoride of formula NR1R2R3R4F, (R represents a hydrogen or alkyl group), and a compound having hydroxyl group, while CO 2 is high pressurized or is preferably kept at a supercritical condition.
- This remover is more effective to remove ashed residues from the semiconductor wafer.
- the fluoride may be any fluoride of formula NR1R2R3R4F where R represents a hydrogen or alkyl group, e.g. ammonium fluoride, tetramethylammoniumfluoride, and tetraethylammoniumfluoride.
- the remover may include the fluoride preferably in the range from 0.001 wt % to 5 wt % of the remover, more preferably in the range from 0.002 wt % to 0.02 wt % of the remover.
- the fluoride is used as the additive to supercritical CO 2 in the presence of a compound having a hydroxyl group, e.g., alcohol (such as ethanol, methanol, n-propanol, isopropanol, n-butanol and isobuthanol, phenol), glycol (such as ethylenglycol and s methylenglycol and polyethylenglycol).
- alcohol is preferred because it effectively dissolves or disperses the fluoride, such as TMAF, homogeneously in supercritical CO 2 .
- ethanol is preferable because a larger amount of the fluoride, such as TMAF, can be dissolved in supercritical CO 2 by the presence of the ethanol.
- the concentration of the compound in supercritical CO 2 depends on the kind and concentration of the fluoride, and the kind of the residue. Approximately, the compound is preferably included in supercritical CO 2 in the range from 1 wt % to 20 wt % of the remover.
- the supercritical CO 2 further comprises dimethyacetamide (hereinafter referred to as "DMAC").
- DMAC dimethyacetamide
- the DMAC contained in the CO 2 is preferably six to seventy times of the fluoride contained in the CO 2 by weight.
- the supercritical CO 2 includes substantially no water, which is a hindrance for manufacturing semiconductor wafers.
- FIG. 1 shows a simplified schematic drawing of an apparatus use for removing residues according to the present invention.
- the semiconductor wafer having residues on its surface is introduced to and placed in a high pressure vessel 9, then CO 2 is supplied from a CO 2 cylinder 1 to the high pressure vessel 9 by a high pressure pump 2.
- the high pressure vessel 9 is thermostated at a specific temperature by a thermostat 10 in order to maintain the pressurized CO 2 in the high pressure vessel 9 at the supercritical condition.
- An additive and a co-solvent are supplied to the high pressure vessel 9 from tanks 3 and 6 by high pressure pumps 4 and 7, respectively, while the additive and co-solvent are mixed by a line mixer 11 on the way to the high pressure vessel 9.
- the flow rates of the additive and the co-solvent are adjusted by valves 5 and 8, respectively in order to set to the predetermined values.
- the CO 2 , the additive and the co-solvent may be supplied continuously.
- Figure 2 shows another embodiment of the apparatus for removing residues according to the present invention.
- the additive is mixed with the co-solvent by the line mixer 11 before being fed into the high pressure vessel 9 in order to avoid heterogeneously contacting.
- the ratio of the additive and the co-solvent to be fed into the high pressure vessel 9 is controlled by a ratio controller 12, which regulates the feeding rate(s) of the additive and/or the co-solvent to the supercritical CO 2 in the high pressure vessel 9.
- the removing process is performed at a temperature in the range from 31°C to 210°C, and at a pressure ranged from 5 M Pa to 30 M Pa, preferably, from 7.1 M Pa to 20 M Pa.
- the time required for removing the residues depends on the size of the object, the kind and amount of the residues, which is usually in the range from a minute to several ten minutes.
- This experiment is carried out by dipping an object in an additive shown in table 1 at an atmospheric pressure at a temperature in the range of from 40°C to 100°C for 20 minutes.
- the object for this experiment is a silicon wafer having a SiO2 layer coated with a novolac phenol type resist, patterned by a development, and treated to form microstructures on its surface by dry etching of a fluorine gas.
- a rate of removing residues is estimated as a ratio of an area of the surface adhering with residues after removing and before removing by a microscope.
- the term "x" and the term “O” mean that the rate is less than 90%, and 90% or more, respectively.
- the term "0" means the rate is 90% or more when the additive is diluted ten times by a co-solvent such as dimethylsulfoxide.
- alkylamine such as methylamine and ethylamine
- alkanolamine such as monoethanolamine
- quaternary ammonium hydroxide such as TMAH and choline
- hydroxylamine and ammonium fluoride
- quaternary ammonium hydroxide, hydroxylamine, and ammonium fluoride have a superior rate for removing residues.
- This experiment for removing residues from the surface of semiconductor wafers is carried out by using a remover including additives H, I, G, J, L, and K which include the fluoride of formula NR1R2R3R4F (R represents a hydrogen or alkyl group).
- the compositions of the additives are listed in Table 4.
- DMAC Dimet ylacetamide
- DIW De-ionized water
- TMAF Tetramethylammoniumfluoride
- PG Propyleneglycol
- DMSO Dimethylsulfoxide
- AcOH Acetic acid
- TBAF Tetrabutylammoniumfluoride
- NH4OAc ammonium acetate.
- silicon wafers A, B and C are used. These silicon wafers have different patterns on their surfaces and the removing characteristics of their resists are also different.
- the silicon wafers are prepared to generate the thermal oxides of silicon on the surface thereof and broken into chips (1cm x 1cm). The chips are etched in the fluoride gas. Then the resists on the chips are ashed by a plasma to generate ashed resists.
- the chips are placed in the high pressure vessel 9.
- the solutions of additives H, I, G, J, K and L are prepared such that the fluoride is dissolved in the other components listed in the table 4, respectively. Then, such additives are introduced with CO 2 and ethanol into the high pressure vessel in Fig. 1.
- the temperature of CO 2 in the high pressure vessel 9 is 40°C
- the pressure is 15 M Pa
- the time for making the chips contact with CO 2 is 3 minutes. After taken out from the high pressure vessel 9, the chips are observed with an electron microscope.
- the ashed resists on the wafer-A are cleaned by both 0.05wt% of H and I with 5wt% ethanol dissolved in the supercritical CO2.
- Excellent means that there is no residues on the surface of the silicon wafer (chips).
- Fair means that there are a few residues on the surface or a little disappearance of the pattern.
- a water rinse is needed to remove residue since a water-soluble residue newly appears on the surface of the silicon wafer (chips).
- Runs 1 to 7 and 9 to 14 the water rinsing step subsequent to the removing step is not needed. In these cases, a solvent including CO 2 and alcohol, e.g.
- Wafer-C contains more difficult ashed resists to be removed from the surface of the silicon wafer (chips). In order to remove this resist, longer removing time (three times longer than wafer-B) is required. The result is excellent.
- the silicon wafers are prepared to generate the thermal oxides of silicon on their surface and are broken into chips.
- the chips are placed in the high pressure vessel 9 in Fig. 1.
- a remover including CO 2 , the additives, and ethanol is introduced into the high pressure vessel 9.
- the chips are taken out and the thickness of the thermal oxides on the chips is measured by an ellipseometer.
- the etch rate of the thermal oxides is determined by dividing the decrease of the thickness per the treatment time.
- the temperature of CO 2 at the supercritical condition is 40C
- the pressure is 15 M Pa
- the treatment time is 20 to 60 minutes.
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Abstract
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Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
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DE60212937T DE60212937T2 (en) | 2001-02-09 | 2002-02-08 | Method for removing residues from the microstructure of an object |
JP2002578549A JP3996513B2 (en) | 2001-02-09 | 2002-02-08 | Method and apparatus for removing residues from microstructures |
KR10-2004-7006269A KR100490506B1 (en) | 2001-02-09 | 2002-02-08 | Composition for removing residues from the microstructure of an object |
EP02736487A EP1358670B1 (en) | 2001-02-09 | 2002-02-08 | Process for removing residues from the microstructure of an object |
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JP2001034337A JP2002237481A (en) | 2001-02-09 | 2001-02-09 | Method of cleaning microscopic structure |
JP2001/034337 | 2001-02-09 |
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US10/240,848 A-371-Of-International US20030106573A1 (en) | 2001-02-09 | 2002-02-08 | Process and apparatus for removing residues from the microstructure of an object |
US10/820,695 Division US20040198627A1 (en) | 2001-02-09 | 2004-04-09 | Process and apparatus for removing residues from the microstructure of an object |
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EP (2) | EP1358670B1 (en) |
JP (2) | JP2002237481A (en) |
KR (2) | KR100482496B1 (en) |
CN (2) | CN1243366C (en) |
AT (2) | ATE332571T1 (en) |
DE (2) | DE60212999T2 (en) |
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WO2003065434A1 (en) | 2002-01-30 | 2003-08-07 | Sony Corporation | Method of treating surface, semiconductor device, process for producing semiconductor device, and apparatus for treatment |
EP1480263A1 (en) * | 2002-01-30 | 2004-11-24 | Sony Corporation | Method of treating surface, semiconductor device, process for producing semiconductor device, and apparatus for treatment |
EP1480263A4 (en) * | 2002-01-30 | 2006-06-07 | Sony Corp | Method of treating surface, semiconductor device, process for producing semiconductor device, and apparatus for treatment |
EP1365441A1 (en) * | 2002-05-23 | 2003-11-26 | Kabushiki Kaisha Kobe Seiko Sho (Kobe Steel, Ltd.) | Process and composition for removing residues from the microstructure of an object |
US7220714B2 (en) | 2002-05-23 | 2007-05-22 | Air Products And Chemicals, Inc. | Process and composition for removing residues from the microstructure of an object |
EP1453080A1 (en) * | 2002-05-23 | 2004-09-01 | Kabushiki Kaisha Kobe Seiko Sho | Process and composition for removing residues from the microstructure of an object |
EP1572833A4 (en) * | 2002-10-31 | 2006-03-15 | Advanced Tech Materials | Supercritical carbon dioxide/chemical formulation for ashed and unashed aluminum post-etch residue removal |
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WO2004042810A1 (en) * | 2002-11-05 | 2004-05-21 | Kabushiki Kaisha Kobe Seiko Sho | Method for cleaning microstructure |
KR100720249B1 (en) * | 2002-11-05 | 2007-05-23 | 가부시키가이샤 고베 세이코쇼 | Method for cleaning microstructure |
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WO2015181313A1 (en) * | 2014-05-28 | 2015-12-03 | Dfd - Dense Fluid Degreasing | Treatment method and device using a supercritical fluid and injection of additive |
FR3021554A1 (en) * | 2014-05-28 | 2015-12-04 | Dfd Dense Fluid Degreasing | METHOD AND DEVICE FOR SUPERCRITICAL FLUID TREATMENT WITH ADDITIVE INJECTION |
Also Published As
Publication number | Publication date |
---|---|
EP1457550B1 (en) | 2006-07-05 |
ATE332355T1 (en) | 2006-07-15 |
WO2002080233A3 (en) | 2002-11-14 |
ATE332571T1 (en) | 2006-07-15 |
KR20040040490A (en) | 2004-05-12 |
EP1457550A2 (en) | 2004-09-15 |
EP1358670A2 (en) | 2003-11-05 |
US20020164873A1 (en) | 2002-11-07 |
CN1542910A (en) | 2004-11-03 |
DE60212937T2 (en) | 2007-12-06 |
DE60212937D1 (en) | 2006-08-17 |
TW569328B (en) | 2004-01-01 |
JP2002237481A (en) | 2002-08-23 |
JP3996513B2 (en) | 2007-10-24 |
KR100490506B1 (en) | 2005-05-19 |
CN1457502A (en) | 2003-11-19 |
SG125957A1 (en) | 2006-10-30 |
KR20020093896A (en) | 2002-12-16 |
US20040198627A1 (en) | 2004-10-07 |
JP2004519863A (en) | 2004-07-02 |
CN1243366C (en) | 2006-02-22 |
KR100482496B1 (en) | 2005-04-14 |
DE60212999T2 (en) | 2006-12-28 |
EP1457550A3 (en) | 2004-11-03 |
DE60212999D1 (en) | 2006-08-17 |
EP1358670B1 (en) | 2006-07-05 |
US20030106573A1 (en) | 2003-06-12 |
EP1358670A4 (en) | 2004-11-17 |
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