US20070072782A1 - Unsaturated dicarboxylic acid and ethylene urea containing formulation for cleaning semiconductor and cleaning method - Google Patents
Unsaturated dicarboxylic acid and ethylene urea containing formulation for cleaning semiconductor and cleaning method Download PDFInfo
- Publication number
- US20070072782A1 US20070072782A1 US10/577,481 US57748104A US2007072782A1 US 20070072782 A1 US20070072782 A1 US 20070072782A1 US 57748104 A US57748104 A US 57748104A US 2007072782 A1 US2007072782 A1 US 2007072782A1
- Authority
- US
- United States
- Prior art keywords
- acid
- weight
- unsaturated dicarboxylic
- formulation
- dicarboxylic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 91
- 238000009472 formulation Methods 0.000 title claims abstract description 89
- 238000000034 method Methods 0.000 title claims abstract description 61
- 238000004140 cleaning Methods 0.000 title claims abstract description 60
- 239000004065 semiconductor Substances 0.000 title claims abstract description 36
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical compound O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 title 1
- 150000001991 dicarboxylic acids Chemical class 0.000 claims abstract description 46
- 150000007514 bases Chemical class 0.000 claims abstract description 20
- 239000002738 chelating agent Substances 0.000 claims abstract description 19
- 239000003960 organic solvent Substances 0.000 claims abstract description 19
- 239000004094 surface-active agent Substances 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims abstract description 15
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims abstract description 15
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 14
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims abstract description 12
- 239000011976 maleic acid Substances 0.000 claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims abstract description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 26
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 24
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 20
- 239000000126 substance Substances 0.000 claims description 20
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 17
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 12
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 10
- 235000019253 formic acid Nutrition 0.000 claims description 10
- 238000004080 punching Methods 0.000 claims description 10
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 9
- RWIVICVCHVMHMU-UHFFFAOYSA-N n-aminoethylmorpholine Chemical compound NCCN1CCOCC1 RWIVICVCHVMHMU-UHFFFAOYSA-N 0.000 claims description 9
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 8
- JPIGSMKDJQPHJC-UHFFFAOYSA-N 1-(2-aminoethoxy)ethanol Chemical compound CC(O)OCCN JPIGSMKDJQPHJC-UHFFFAOYSA-N 0.000 claims description 8
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 8
- KKFDCBRMNNSAAW-UHFFFAOYSA-N 2-(morpholin-4-yl)ethanol Chemical compound OCCN1CCOCC1 KKFDCBRMNNSAAW-UHFFFAOYSA-N 0.000 claims description 8
- YSAANLSYLSUVHB-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]ethanol Chemical compound CN(C)CCOCCO YSAANLSYLSUVHB-UHFFFAOYSA-N 0.000 claims description 8
- WFCSWCVEJLETKA-UHFFFAOYSA-N 2-piperazin-1-ylethanol Chemical compound OCCN1CCNCC1 WFCSWCVEJLETKA-UHFFFAOYSA-N 0.000 claims description 8
- UIKUBYKUYUSRSM-UHFFFAOYSA-N 3-morpholinopropylamine Chemical compound NCCCN1CCOCC1 UIKUBYKUYUSRSM-UHFFFAOYSA-N 0.000 claims description 8
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 8
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 claims description 8
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 claims description 8
- 235000019260 propionic acid Nutrition 0.000 claims description 8
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 8
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 8
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 5
- 229930195725 Mannitol Natural products 0.000 claims description 5
- 239000000174 gluconic acid Substances 0.000 claims description 5
- 235000012208 gluconic acid Nutrition 0.000 claims description 5
- 239000000594 mannitol Substances 0.000 claims description 5
- 235000010355 mannitol Nutrition 0.000 claims description 5
- 238000005498 polishing Methods 0.000 claims description 5
- GEWWCWZGHNIUBW-UHFFFAOYSA-N 1-(4-nitrophenyl)propan-2-one Chemical compound CC(=O)CC1=CC=C([N+]([O-])=O)C=C1 GEWWCWZGHNIUBW-UHFFFAOYSA-N 0.000 claims description 4
- HWJSDSLWRKEWOL-UHFFFAOYSA-N 3-(2-aminoethylamino)-2-methylpropanenitrile Chemical compound N#CC(C)CNCCN HWJSDSLWRKEWOL-UHFFFAOYSA-N 0.000 claims description 4
- NSQSYCXRUVZPKI-UHFFFAOYSA-N 3-(2-aminoethylamino)propanenitrile Chemical compound NCCNCCC#N NSQSYCXRUVZPKI-UHFFFAOYSA-N 0.000 claims description 4
- VZKSLWJLGAGPIU-UHFFFAOYSA-N 3-morpholin-4-ylpropan-1-ol Chemical compound OCCCN1CCOCC1 VZKSLWJLGAGPIU-UHFFFAOYSA-N 0.000 claims description 4
- UVLSCMIEPPWCHZ-UHFFFAOYSA-N 3-piperazin-1-ylpropan-1-amine Chemical compound NCCCN1CCNCC1 UVLSCMIEPPWCHZ-UHFFFAOYSA-N 0.000 claims description 4
- LWEOFVINMVZGAS-UHFFFAOYSA-N 3-piperazin-1-ylpropan-1-ol Chemical compound OCCCN1CCNCC1 LWEOFVINMVZGAS-UHFFFAOYSA-N 0.000 claims description 4
- -1 C1-10alkyl glucoside Chemical class 0.000 claims description 4
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 4
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 239000011668 ascorbic acid Substances 0.000 claims description 4
- 235000010323 ascorbic acid Nutrition 0.000 claims description 4
- 229960005070 ascorbic acid Drugs 0.000 claims description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004327 boric acid Substances 0.000 claims description 4
- 235000010338 boric acid Nutrition 0.000 claims description 4
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 claims description 4
- 229940018557 citraconic acid Drugs 0.000 claims description 4
- 229930182478 glucoside Natural products 0.000 claims description 4
- 239000000600 sorbitol Substances 0.000 claims description 4
- 235000010356 sorbitol Nutrition 0.000 claims description 4
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims 3
- 239000007864 aqueous solution Substances 0.000 claims 3
- 150000001735 carboxylic acids Chemical class 0.000 abstract description 3
- 235000012431 wafers Nutrition 0.000 description 48
- 239000010410 layer Substances 0.000 description 23
- 239000012212 insulator Substances 0.000 description 13
- 239000011229 interlayer Substances 0.000 description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 11
- 229910052802 copper Inorganic materials 0.000 description 11
- 239000010949 copper Substances 0.000 description 11
- 238000004380 ashing Methods 0.000 description 10
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 9
- 239000005751 Copper oxide Substances 0.000 description 9
- 229910000431 copper oxide Inorganic materials 0.000 description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 6
- 229920002120 photoresistant polymer Polymers 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000009977 dual effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 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 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 238000001312 dry etching Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- LLQHSBBZNDXTIV-UHFFFAOYSA-N 6-[5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-4,5-dihydro-1,2-oxazol-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC1CC(=NO1)C1=CC2=C(NC(O2)=O)C=C1 LLQHSBBZNDXTIV-UHFFFAOYSA-N 0.000 description 1
- 229910021594 Copper(II) fluoride Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- GWFAVIIMQDUCRA-UHFFFAOYSA-L copper(ii) fluoride Chemical compound [F-].[F-].[Cu+2] GWFAVIIMQDUCRA-UHFFFAOYSA-L 0.000 description 1
- 229940073499 decyl glucoside Drugs 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- QAULOJGTCHPJSY-UHFFFAOYSA-N ethene;imidazolidin-2-one;urea Chemical compound C=C.NC(N)=O.O=C1NCCN1 QAULOJGTCHPJSY-UHFFFAOYSA-N 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- HOVAGTYPODGVJG-UHFFFAOYSA-N methyl beta-galactoside Natural products COC1OC(CO)C(O)C(O)C1O HOVAGTYPODGVJG-UHFFFAOYSA-N 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/24—Cleaning or pickling metallic material with solutions or molten salts with neutral solutions
-
- 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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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
- H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/662—Carbohydrates or derivatives
-
- 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2082—Polycarboxylic acids-salts thereof
-
- 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/32—Amides; Substituted amides
- C11D3/323—Amides; Substituted amides urea or derivatives thereof
-
- 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
- C11D7/22—Organic compounds
- C11D7/26—Organic compounds containing oxygen
- C11D7/265—Carboxylic acids or salts thereof
-
- 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
- C11D7/3272—Urea, guanidine or derivatives thereof
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
- G03F7/422—Stripping or agents therefor using liquids only
-
- 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
- H01L21/0206—Cleaning during device manufacture during, before or after processing of insulating layers
- H01L21/02063—Cleaning during device manufacture during, before or after processing of insulating layers the processing being the formation of vias or contact holes
-
- 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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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
-
- C11D2111/22—
-
- 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2003—Alcohols; Phenols
- C11D3/2041—Dihydric alcohols
- C11D3/2044—Dihydric alcohols linear
Definitions
- the present invention relates generally to a chemical formulation used in semiconductor wafer fabrication and particularly to a chemical formulation that is utilized to remove residue from wafers following plasma ashing of a photoresist. More specifically, the present invention relates to a chemical formulation for removal of residue from semiconductor wafers containing chemically delicate copper interconnect and low-k or ultra low-k interlayer insulator layers.
- semiconductor wafers are being developed by using copper interconnect material for reducing wiring resistance and by using low-k interlayer insulator layers (low-k film) or ultra low-k interlayer insulator layers (ultra low-k film) having a k-value of 3.0 or less for reducing interconnect capacity.
- Representative wafers include single damascene or dual damascene wafers.
- Pattern formation by use of interconnect material, interlayer insulator layer material or the like is mainly carried out by dry etching by utilizing a photoresist as a mask and then plasma ashing for removal of the photoresist.
- Patent Document 1 U.S. Pat. No. 5,334,332
- Patent Document 2 EP patent No. 662705
- a semiconductor wafer cleaning formulation for use in semiconductor fabrication comprising (a) an unsaturated dicarboxylic acid, and (b) ethylene urea (2-imidazolidone);
- each component of the formulation is suitably determined depending on the object to be removed, but the following amount is preferable:
- Preferable basic compounds (d) are:
- TMAPEA trimethylaminopropylethanolamine
- Preferable surfactants (h) are:
- the formulation has pH of 1 to 5, preferably 2 to 4.
- Treatment temperature of the formulation is not specifically limited while it could remove residue completely.
- the treatment temperature of 21-40° C. affords sufficient effect.
- Treatment time of the formulation is not specifically limited while it could remove residue completely.
- the treatment time of 1-5 min affords sufficient effect.
- Treatment procedure of the formulation is not specifically limited while it contact to the wafer containing residues.
- the formulation can be suitably applied to batch process or single wafer process.
- the formulation can be used for residue removal of wafers in semiconductor fabrication, for example it is useful for (1) a cleaning process after making via hole, (2) a cleaning process after making trench, (3) a cleaning process after punching of etch stopper layer, or (4) a cleaning process after CMP (chemical mechanical polishing).
- CMP chemical mechanical polishing
- Copper blanket wafers were treated with O2 plasma (250° C., 120 sec) and the resulting copper oxide wafers were used for test. Each wafer was immersed into any one of formulations of Examples 1-15 and Comparative Examples 1-6 at 40° C. for 2 min. After that each wafer was rinsed with deionized water and air-dried. Copper oxide removal ability was determined with optical microscopic observation and a qualitative analysis of oxidization state of copper on wafer surface measured with X-ray photoelectron spectroscopy (XPS; Shimadzu ESCA-3200).
- XPS X-ray photoelectron spectroscopy
- Preferable formulations of the present invention could completely remove punching residue of etch stopper layer without any damage on copper, or low-k or ultra low-k interlayer insulator layer. Further, etching residue of low-k or ultra low-k interlayer insulator layer could also be completely removed.
- the preferable formulations indicate the most excellent results, and have comparable performance each other when they are evaluated based on both removable ability and low corrosivity as a whole.
Abstract
A semiconductor wafer cleaning formulation comprising an unsaturated dicarboxylic acid and ethylene urea, and a cleaning method are provided. The formulation comprises an unsaturated dicarboxylic acid and ethylene urea as essential components, and is used for removing residues in semiconductor fabrication. As the unsaturated dicarboxylic acid, maleic acid is particularly preferable. The preferred formulation comprises an unsaturated dicarboxylic acid, ethylene urea, at least one organic carboxylic acid except unsaturated dicarboxylic acid, at least one basic compound except ethylene urea and water. The formulation can optionally comprise at least one selected from the group consisting of an organic solvent, a chelating agent, a surfactant, and phosphonic acid and/or phosphinic acid.
Description
- The present invention relates generally to a chemical formulation used in semiconductor wafer fabrication and particularly to a chemical formulation that is utilized to remove residue from wafers following plasma ashing of a photoresist. More specifically, the present invention relates to a chemical formulation for removal of residue from semiconductor wafers containing chemically delicate copper interconnect and low-k or ultra low-k interlayer insulator layers.
- As semiconductor wafer designs recently become smaller, semiconductor wafers are being developed by using copper interconnect material for reducing wiring resistance and by using low-k interlayer insulator layers (low-k film) or ultra low-k interlayer insulator layers (ultra low-k film) having a k-value of 3.0 or less for reducing interconnect capacity. Representative wafers include single damascene or dual damascene wafers.
- Pattern formation by use of interconnect material, interlayer insulator layer material or the like is mainly carried out by dry etching by utilizing a photoresist as a mask and then plasma ashing for removal of the photoresist.
- The prior art tells the utilization of various chemical formulations to remove residue and clean wafers following a plasma ashing process. Most of these prior art chemical formulations are based on alkaline amines (for example, see Patent Document 1) and fluorine compounds (for example, see Patent Document 2). Still other chemical formulations are based on organic carboxylic acids (for example, see Patent Document 3).
- Patent Document 1: U.S. Pat. No. 5,334,332
- Patent Document 2: EP patent No. 662705
- Patent Document 3: US publication No. 2003/0143495 A1
- Problem to be Solved by the Invention
- These various prior art chemical formulations have drawbacks that often include unwanted removal of wiring metal such as copper or low-k and ultra low-k insulator layers. There is therefore a need for chemical formulations that effectively remove residue following a resist ashing process and do not affect on wiring metal and low-k and ultra low-k interlayer insulator layers.
- Means for Solving the Problem
- The present invention relates generally to a chemical formulation used in semiconductor wafer fabrication and particularly to a chemical formulation that is utilized to remove residue from wafers following a plasma ashing process of photoresist. Namely, the present invention relates to the following invention [1] to [12]:
- [1] A semiconductor wafer cleaning formulation for use in semiconductor fabrication comprising (a) an unsaturated dicarboxylic acid, and (b) ethylene urea (2-imidazolidone);
- [2] The cleaning formulation as described in [1], further comprising (c) at least one organic carboxylic acid except unsaturated dicarboxylic acid, (d) at least one basic compound except ethylene urea, and (e) water;
- [3] The cleaning formulation as described in [2], further comprising at least one selected from the group consisting of (e an organic solvent, (g) a chelating agent, (h) a surfactant, and (i) phosphonic acid and/or phosphinic acid;
- [4] The cleaning formulation as described in [1]-[3], comprising each component (a) to (i) in the following amount shown in percentage by weight based on total weight of the formulation:
(a) an unsaturated dicarboxylic acid 1-9% by weight (b) ethylene urea 1-20% by weight (c) at least one organic carboxylic acid except 1-20% by weight unsaturated dicarboxylic acid (d) at least one basic compound except ethylene 0.1-50% by weight urea (e) water 2-90% by weight (f) an organic solvent 1-20 by weight (g) a chelating agent 0.01-5% by weight (h) a surfactant 0.01-0.2% by weight (i) phosphonic acid and/or phosphinic acid 0.5-5% by weight;
[5] A method for cleaning a semiconductor wafer comprising cleaning the wafer by using a semiconductor wafer cleaning formulation comprising (a) an unsaturated dicarboxylic acid, and (b) ethylene urea, in semiconductor fabrication;
[6] The method for cleaning a semiconductor wafer described in [5], wherein the semiconductor wafer cleaning formulation further comprising (c) at least one organic carboxylic acid except unsaturated dicarboxylic acid, (d) at least one basic compound except ethylene urea, and (e) water is used;
[7] The method for cleaning a semiconductor wafer described in [6], wherein the semiconductor wafer cleaning formulation further comprising at least one selected from the group consisting of (f) an organic solvent, (g) a chelating agent, (h) a surfactant, and (i) phosphonic acid and/or phosphinic acid is used; - [8] The method for cleaning a semiconductor wafer described in [5]-[7], wherein the semiconductor wafer cleaning formulation comprising each component (a) to (i) in the following amount shown in percentage by weight based on total weight of the formulation is used:
(a) an unsaturated dicarboxylic acid 1-9% by weight (b) ethylene urea 1-20% by weight (c) at least one organic carboxylic acid 1-20% by weight except unsaturated dicarboxylic acid (d) at least one basic compound except ethylene 0.1-50% by weight urea (e) water 2-90% by weight (f) an organic solvent 1-20 by weight (g) a chelating agent 0.01-5% by weight (h) a surfactant 0.01-0.2% by weight (i) phosphonic acid and/or phosphinic acid 0.5-5% by weight;
[9] A method for cleaning a semiconductor wafer comprising cleaning the wafer by using a semiconductor wafer cleaning formulation comprising (a) an unsaturated dicarboxylic acid, and (b) ethylene urea, in (1) a cleaning process after making via hole, (2) a cleaning process after making trench, (3) a cleaning process after punching of etch stopper layer, or (4) a cleaning process after CMP (chemical mechanical polishing) among semiconductor fabrication;
[10] The method for cleaning a semiconductor wafer described in [9], wherein the semiconductor wafer cleaning formulation further comprising (c) at least one organic carboxylic acid except unsaturated dicarboxylic acid, (d) at least one basic compound except ethylene urea, and (e) water is used;
[11] The method for cleaning a semiconductor wafer described in [9], wherein the semiconductor wafer cleaning formulation further comprising at least one selected from the group consisting of (f) an organic solvent, (g) a chelating agent, (h) a surfactant, and (i) phosphonic acid and/or phosphinic acid is used; - [12] The method for cleaning a semiconductor wafer described in [9]-[11], wherein the semiconductor wafer cleaning formulation comprising each component (a) to (i) in the following amount shown in percentage by weight based on total weight of the formulation is used:
(a) an unsaturated dicarboxylic acid 1-9% by weight (b) ethylene urea 1-20% by weight (c) at least one organic carboxylic acid except 1-20% by weight unsaturated dicarboxylic acid (d) at least one basic compound except ethylene 0.1-50% by weight urea (e) water 2-90% by weight (f) an organic solvent 1-20 by weight (g) a chelating agent 0.01-5% by weight (h) a surfactant 0.01-0.2% by weight (i) phosphonic acid and/or phosphinic acid 0.5-5% by weight. - The chemical formulation of the present invention is effective for removing residues from wafers formed in semiconductor wafer fabrication, particularly for removing all residue from wafers following a plasma ashing process. Especially, these formulations are effective in the cleaning of dual damascene wafer. Fabrication processes of dual damascene structure wafer are as follows: (i) after depositions of interlayer insulator layer, etch stopper layer and photoresist, and son on, a via hole is constructed by dry etching and plasma ashing; (ii) filling a photoresist or other material in the via hole, and trench structure is constructed by the same process as above; (iii) etch stopper layer is removed by punching; and (iv) after filling copper into the via hole and trench together, overfilled copper is polished by CMP (chemical mechanical polishing). After each of (i) to (iv) processes, cleaning processes are carried out. The formulation of the present invention is effective in all of the cleaning processes.
- That is, it is an advantage of the formulation of the present invention that it effectively removes residue following a plasma ashing process.
- It is another advantage of the formulation that it can effectively remove especially etch stopper layer punching residues. Generally, the etch stopper layer punching residues are often difficult to be completely removed without any damage on copper and low-k and ultra low-k interlayer insulator layers. But the formulation can remove such etch residues without any damage thereon.
- It is a further advantage of the formulation that it effectively removes metal oxide like copper oxide or metal halides like copper fluoride following plasma ashing.
- It is a further advantage of the formulation that it effectively removes metal oxide like copper oxide remaining after CMP (chemical mechanical polishing).
- It is yet another advantage of the formulation that it provides residue removal performance with less corrosivity on copper than conventional acidic cleaning solutions.
- It is yet a further advantage of the formulation that it provides residue removal performance with less corrosivity on low-k and ultra low-k interlayer insulator layers than conventional amine-based and ammonium fluoride-based cleaning solutions.
- It is yet another advantage of the formulation that it provides residue removal performance with lower temperature than conventional amine-based and ammonium fluoride-based cleaning solutions.
- It is yet a further advantage of the formulation that it provides residue removal performance with shorter treatment time than conventional amine-based and ammonium fluoride-based chemicals.
- These and other features and advantages of the formulation will become understood to those of ordinary skill in the art upon review of the following detailed description of the preferred embodiments.
- The present invention relates to a chemical formulation that is suitable for removing residues originating from dry etching and plasma ashing, or the like in semiconductor wafer fabrication. The formulation comprises (a) an unsaturated dicarboxylic acid, and (b) ethylene urea, as essential components. Among (a) the unsaturated dicarboxylic acids, maleic acid is particularly preferable. The composition preferably comprises (a) an unsaturated dicarboxylic acid, (b) ethylene urea, (c) at least one organic carboxylic acid except unsaturated dicarboxylic acid, (d) at least one basic compound except ethylene urea, and (e) water. In addition, the preferable composition may contain at least one selected from the group consisting of (f) an organic solvent, (g) a chelating agent, (h) a surfactant, and (i) phosphonic acid and/or phosphinic acid.
- The amount shown in percentage by weight (based on total weight of the formulation) of each component of the formulation is suitably determined depending on the object to be removed, but the following amount is preferable:
- (a) an unsaturated dicarboxylic acid 1-9% by weight
- (b) ethylene urea 1-20% by weight
- (c) at least one organic carboxylic acid except unsaturated dicarboxylic acid 1-20% by weight
- (d) at least one basic compound except ethylene urea 0.1-50% by weight
- (e) water 2-90% by weight
- (f) an organic solvent 1-20 by weight
- (g) a chelating agent 0.01-5% by weight
- (h) a surfactant 0.01-0.2% by weight
- (i) phosphonic acid and/or phosphinic acid 0.5-5% by weight
- Preferable unsaturated dicarboxylic acids (a) are
- (a-1) maleic acid, and
- (a-2) citraconic acid, particularly preferable unsaturated dicarboxylic acids (a) is
- (a-1) maleic acid.
- Preferable organic carboxylic acids (c) are
- (c-1) formic acid (FA),
- (c-2) acetic acid (AA), and
- (c-3) propionic acid (PA).
- Preferable basic compounds (d) are
- (d-1) hydroxyethylpiperazine (HEP),
- (d-2) hydroxypropylpiperazine (HPP),
- (d-3) aminoethylpiperazine (AEP),
- (d-4) aminopropylpiperazine (APP),
- (d-5) hydroxyethylmorpholine (HEM),
- (d-6 hydroxypropylmorpholine (HPM),
- (d-7) aminoethylmorpholine (AEM),
- (d-8) aminopropylmorpholine (APM),
- (d-9) triethanolamine (TEA),
- (d-10) pentamethyldiethylenetriamine (PMDETA),
- (d-11) dimethylaminoethoxyethanol (DMAEE),
- (d-12) aminoethoxyethanol (AEE),
- (d-13) trimethylaminoethylethanolamine (TMAEEA),
- (d-14) trimethylaminopropylethanolamine (TMAPEA),
- (d-15) N-(2-cyanoethyl)ethylenediamine (CEEDA),
- (d-16) N-(2-cyanopropyl)ethylenediamine (CPEDA). and
- (d-17) ammonia (NH3).
- Preferable organic solvents (f) are
- (f-1) 1,4-butanediol (1,4-BD),
- (f-2) 1,3-butanediol (1,3-BD),
- (f-3) ethylene glycol (EG),
- (f-4) propylene glycol (PG),
- (f-5) N-methylpyrrolidone (NMP),
- (f-6) γ-butyrolactone (GBL),
- (f-7) propylene glycol monomethylether (PGME), and
- (f-8) propylene glycol monomethylether acetate (PGMEA).
- Preferable chelating agents (g) are
- (g-1) ascorbic acid,
- (g-2) gluconic acid,
- (g-3) mannitol,
- (g-4) sorbitol, and
- (g-5) boric acid.
- Preferable surfactants (h) are
- (h-1) C1-10alkyl glucosides.
- Each component in the formulation included in the present invention can be arbitrarily combined. Combinations of each component include for example those shown in the following table. In the meantime, the table is shown for purposes of illustration, and the present invention is not limited to these combinations.
(a) (b) (c) (d) (e) (a-1) (b) (c-1) (d-1) (e) (a-1) (b) (c-1) (d-2) (e) (a-1) (b) (c-1) (d-3) (e) (a-1) (b) (c-1) (d-4) (e) (a-1) (b) (c-1) (d-5) (e) (a-1) (b) (c-1) (d-6) (e) (a-1) (b) (c-1) (d-7) (e) (a-1) (b) (c-1) (d-8) (e) (a-1) (b) (c-1) (d-9) (e) (a-1) (b) (c-1) (d-10) (e) (a-1) (b) (c-1) (d-11) (e) (a-1) (b) (c-1) (d-12) (e) (a-1) (b) (c-1) (d-13) (e) (a-1) (b) (c-1) (d-14) (e) (a-1) (b) (c-1) (d-15) (e) (a-1) (b) (c-1) (d-16) (e) (a-1) (b) (c-1) (d-17) (e) (a-1) (b) (c-2) (d-1) (e) (a-1) (b) (c-2) (d-2) (e) (a-1) (b) (c-2) (d-3) (e) (a-1) (b) (c-2) (d-4) (e) (a-1) (b) (c-2) (d-5) (e) (a-1) (b) (c-2) (d-6) (e) (a-1) (b) (c-2) (d-7) (e) (a-1) (b) (c-2) (d-8) (e) (a-1) (b) (c-2) (d-9) (e) (a-1) (b) (c-2) (d-10) (e) (a-1) (b) (c-2) (d-11) (e) (a-1) (b) (c-2) (d-12) (e) (a-1) (b) (c-2) (d-13) (e) (a-1) (b) (c-2) (d-14) (e) (a-1) (b) (c-2) (d-15) (e) (a-1) (b) (c-2) (d-16) (e) (a-1) (b) (c-2) (d-17) (e) (a-1) (b) (c-3) (d-1) (e) (a-1) (b) (c-3) (d-2) (e) (a-1) (b) (c-3) (d-3) (e) (a-1) (b) (c-3) (d-4) (e) (a-1) (b) (c-3) (d-5) (e) (a-1) (b) (c-3) (d-6) (e) (a-1) (b) (c-3) (d-7) (e) (a-1) (b) (c-3) (d-8) (e) (a-1) (b) (c-3) (d-9) (e) (a-1) (b) (c-3) (d-10) (e) (a-1) (b) (c-3) (d-11) (e) (a-1) (b) (c-3) (d-12) (e) (a-1) (b) (c-3) (d-13) (e) (a-1) (b) (c-3) (d-14) (e) (a-1) (b) (c-3) (d-15) (e) (a-1) (b) (c-3) (d-16) (e) (a-1) (b) (c-3) (d-17) (e) (a-1) (b) (c-1) (d-1)(d-2) (e) (a-1) (b) (c-1) (d-1)(d-3) (e) (a-1) (b) (c-1) (d-1)(d-4) (e) (a-1) (b) (c-1) (d-1)(d-5) (e) (a-1) (b) (c-1) (d-1)(d-6) (e) (a-1) (b) (c-1) (d-1)(d-7) (e) (a-1) (b) (c-1) (d-1)(d-8) (e) (a-1) (b) (c-1) (d-1)(d-9) (e) (a-1) (b) (c-1) (d-1)(d-10) (e) (a-1) (b) (c-1) (d-1)(d-11) (e) (a-1) (b) (c-1) (d-1)(d-12) (e) (a-1) (b) (c-1) (d-1)(d-13) (e) (a-1) (b) (c-1) (d-1)(d-14) (e) (a-1) (b) (c-1) (d-1)(d-15) (e) (a-1) (b) (c-1) (d-1)(d-16) (e) (a-1) (b) (c-1) (d-1)(d-17) (e) (a-1) (b) (c-1) (d-2)(d-1) (e) (a-1) (b) (c-1) (d-2)(d-3) (e) (a-1) (b) (c-1) (d-2)(d-4) (e) (a-1) (b) (c-1) (d-2)(d-5) (e) (a-1) (b) (c-1) (d-2)(d-6) (e) (a-1) (b) (c-1) (d-2)(d-7) (e) (a-1) (b) (c-1) (d-2)(d-8) (e) (a-1) (b) (c-1) (d-2)(d-9) (e) (a-1) (b) (c-1) (d-2)(d-10) (e) (a-1) (b) (c-1) (d-2)(d-11) (e) (a-1) (b) (c-1) (d-2)(d-12) (e) (a-1) (b) (c-1) (d-2)(d-13) (e) (a-1) (b) (c-1) (d-2)(d-14) (e) (a-1) (b) (c-1) (d-2)(d-15) (e) (a-1) (b) (c-1) (d-2)(d-16) (e) (a-1) (b) (c-1) (d-2)(d-17) (e) (a-1) (b) (c-1) (d-3)(d-1) (e) (a-1) (b) (c-1) (d-3)(d-2) (e) (a-1) (b) (c-1) (d-3)(d-4) (e) (a-1) (b) (c-1) (d-3)(d-5) (e) (a-1) (b) (c-1) (d-3)(d-6) (e) (a-1) (b) (c-1) (d-3)(d-7) (e) (a-1) (b) (c-1) (d-3)(d-8) (e) (a-1) (b) (c-1) (d-3)(d-9) (e) (a-1) (b) (c-1) (d-3)(d-10) (e) (a-1) (b) (c-1) (d-3)(d-11) (e) (a-1) (b) (c-1) (d-3)(d-12) (e) (a-1) (b) (c-1) (d-3)(d-13) (e) (a-1) (b) (c-1) (d-3)(d-14) (e) (a-1) (b) (c-1) (d-3)(d-15) (e) (a-1) (b) (c-1) (d-3)(d-16) (e) (a-1) (b) (c-1) (d-3)(d-17) (e) (a-1) (b) (c-1) (d-4)(d-1) (e) (a-1) (b) (c-1) (d-4)(d-2) (e) (a-1) (b) (c-1) (d-4)(d-3) (e) (a-1) (b) (c-1) (d-4)(d-5) (e) (a-1) (b) (c-1) (d-4)(d-6) (e) (a-1) (b) (c-1) (d-4)(d-7) (e) (a-1) (b) (c-1) (d-4)(d-8) (e) (a-1) (b) (c-1) (d-4)(d-9) (e) (a-1) (b) (c-1) (d-4)(d-10) (e) (a-1) (b) (c-1) (d-4)(d-11) (e) (a-1) (b) (c-1) (d-4)(d-12) (e) (a-1) (b) (c-1) (d-4)(d-13) (e) (a-1) (b) (c-1) (d-4)(d-14) (e) (a-1) (b) (c-1) (d-4)(d-15) (e) (a-1) (b) (c-1) (d-4)(d-16) (e) (a-1) (b) (c-1) (d-4)(d-17) (e) (a-1) (b) (c-1) (d-5)(d-1) (e) (a-1) (b) (c-1) (d-5)(d-2) (e) (a-1) (b) (c-1) (d-5)(d-3) (e) (a-1) (b) (c-1) (d-5)(d-4) (e) (a-1) (b) (c-1) (d-5)(d-6) (e) (a-1) (b) (c-1) (d-5)(d-7) (e) (a-1) (b) (c-1) (d-5)(d-8) (e) (a-1) (b) (c-1) (d-5)(d-9) (e) (a-1) (b) (c-1) (d-5)(d-10) (e) (a-1) (b) (c-1) (d-5)(d-11) (e) (a-1) (b) (c-1) (d-5)(d-12) (e) (a-1) (b) (c-1) (d-5)(d-13) (e) (a-1) (b) (c-1) (d-5)(d-14) (e) (a-1) (b) (c-1) (d-5)(d-15) (e) (a-1) (b) (c-1) (d-5)(d-16) (e) (a-1) (b) (c-1) (d-5)(d-17) (e) (a-1) (b) (c-1) (d-6)(d-1) (e) (a-1) (b) (c-1) (d-6)(d-2) (e) (a-1) (b) (c-1) (d-6)(d-3) (e) (a-1) 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(d-17)(d-14) (e) (a-1) (b) (c-1) (d-17)(d-15) (e) (a-1) (b) (c-1) (d-17)(d-16) (e) - The formulation has pH of 1 to 5, preferably 2 to 4.
- Treatment temperature of the formulation is not specifically limited while it could remove residue completely. For example, the treatment temperature of 21-40° C. affords sufficient effect.
- Treatment time of the formulation is not specifically limited while it could remove residue completely. For example, the treatment time of 1-5 min affords sufficient effect.
- Treatment procedure of the formulation is not specifically limited while it contact to the wafer containing residues. The formulation can be suitably applied to batch process or single wafer process.
- In addition, the formulation can be used for residue removal of wafers in semiconductor fabrication, for example it is useful for (1) a cleaning process after making via hole, (2) a cleaning process after making trench, (3) a cleaning process after punching of etch stopper layer, or (4) a cleaning process after CMP (chemical mechanical polishing).
- The present invention is explained with some examples described below, but this invention is not limited to these examples.
- (1) Copper Oxide Removal Test
- Copper blanket wafers were treated with O2 plasma (250° C., 120 sec) and the resulting copper oxide wafers were used for test. Each wafer was immersed into any one of formulations of Examples 1-15 and Comparative Examples 1-6 at 40° C. for 2 min. After that each wafer was rinsed with deionized water and air-dried. Copper oxide removal ability was determined with optical microscopic observation and a qualitative analysis of oxidization state of copper on wafer surface measured with X-ray photoelectron spectroscopy (XPS; Shimadzu ESCA-3200).
- The components of Examples 1-15 and Comparative Example 1-6, and the test results are shown in Tables 1-3. And copper oxide removal ability were estimated as follows:
- ◯: Yellow colored surface of wafer (from optical microscopic observation), no Cu2+ peaks in XPS spectra.
- X: Red colored surface of wafer (from optical microscopic observation), remain of Cu2+ peaks in XPS spectra.
TABLE 1 (Each value shows % by weight based on the total formulation) Example 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 Water 55 55 55 55 55 55 55 55 55 55 55 55 55 78.8 78.8 Maleic acid 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 Ethylene urea 5 5 20 5 5 5 5 5 5 5 5 5 5 5 5 Formic acid 10 10 10 10 10 10 10 10 10 10 10 10 10 4.2 4.2 1,4-Buthanediol — — — — — 5 5 — — — — — — — — Ethylene glycol — — — — — — — 5 5 — — — — — — TEA 20 20 5 — — — — 15 15 15 15 20 20 5 5 TMAEEA — — — 20 20 15 15 — — — — — — — — AEM 5 — 5 5 — 5 — 5 — 5 5 5 5 — — AEP — 5 — — 5 — 5 — 5 — — — — — — NH3 — — — — — — — — — — — — — 1.2 1.2 Gluconic acid — — — — — — — — — 5 — — — — Mannitol — — — — — — — — — — 5 — — — — Methyl glucoside — — — — — — — — — — — 0.15 — — — Decyl glucoside — — — — — — — — — — — — 0.15 — — Phosphonic acid — — — — — — — — — — — — — 0.8 — Phosphinic acid — — — — — — — — — — — — — — 0.8 Copper oxide ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ removal -
TABLE 2 (Each value shows % by weight based on the total formulation) Comparative Example 1 2 3 4 Water 55 55 55 55 Maleic acid — — 5 10 Malonic acid 5 — — — Acrylic acid — 5 — — Ethylene urea 5 5 — 5 Formic acid 10 10 — 5 TEA 20 20 20 20 AEM 5 5 15 5 Copper oxide x x x x removal -
TABLE 3 (Each value shows % by weight based on the total formulation) Comparative Example 5 6 Water 29 — NH4F 1 — Dimethylacetamide 60 — Diethylene glycol- 10 — monomethylether Monoethanolamine — 30 Dimethylsulfoxide — 70 Copper oxide x x removal
(2) Removal Test for Punching Residue of Low-k and Ultra Low-k Interlayer Insulator Layer and Etch Stopper Layer - Wafers for cleaning evaluation of dual damascene or single damascene structure having punching residue of etch stopper layer were used for evaluation of the formulation of the present invention. The wafers were immersed into any one of the formulations at 40° C. for 5 min. After each wafer was rinsed with deionized water and air-dried, removal ability of punching residue of the etch stopper layer and corrosivity of copper, or low-k or ultra low-k interlayer insulator layer were determined with scanning electron microscopic (SEM) observation.
- Preferable formulations of the present invention could completely remove punching residue of etch stopper layer without any damage on copper, or low-k or ultra low-k interlayer insulator layer. Further, etching residue of low-k or ultra low-k interlayer insulator layer could also be completely removed. The preferable formulations indicate the most excellent results, and have comparable performance each other when they are evaluated based on both removable ability and low corrosivity as a whole.
- While the present invention has been described with reference to certain preferred embodiments, it will be understood by those skilled in the art that various alternations and modifications may be made therein without departing from the true spirit and scope of the invention. It is therefore intended that the following claims cover all such alternations and modifications, which nevertheless include the true spirit and scope of the invention.
Claims (42)
1. A semiconductor wafer cleaning formulation for use in semiconductor fabrication comprising an unsaturated dicarboxylic acid, and ethylene urea.
2. The cleaning formulation according to claim 1 , wherein the formulation is an aqueous solution.
3. The cleaning formulation according to claim 2 , comprising
1-9% by weight of an unsaturated dicarboxylic acid; and
1-20% by weight of ethylene urea.
4. The cleaning formulation according to claim 2 , further comprising
at least one organic carboxylic acid except unsaturated dicarboxylic acid, and
at least one basic compound except ethylene urea.
5. The cleaning formulation according to claim 4 , comprising
1-9% by weight of an unsaturated dicarboxylic acid;
1-20% by weight of ethylene urea;
1-20% by weight of at least one organic carboxylic acid except unsaturated dicarboxylic acid;
0.1-50% by weight of at least one basic compound except ethylene urea; and
20-90% by weight of water.
6. The cleaning formulation according to claim 4 , wherein the unsaturated dicarboxylic acid is selected from the group consisting of maleic acid and citraconic acid.
7. The cleaning formulation according to claim 4 , wherein the unsaturated dicarboxylic acid is maleic acid.
8. The cleaning formulation according to claim 4 , wherein the organic carboxylic acid is selected from the group consisting of:
formic acid (FA),
acetic acid (AA), and
propionic acid (PA).
9. The cleaning formulation according to claim 4 , wherein the basic compound is selected from the group consisting of:
hydroxyethylpiperazine (HEP),
hydroxypropylpiperazine (HPP),
aminoethylpiperazine (AEP),
aminopropylpiperazine (APP),
hydroxyethylmorpholine (HEM),
hydroxypropylmorpholine (HPM),
aminoethylmorpholine (AEM),
aminopropylmorpholine (APM),
triethanolamine (TEA),
pentamethyldiethylenetriamine (PMDETA),
dimethylaminoethoxyethanol (DMAEE),
aminoethoxyethanol (AEE),
trimethylaminoethylethanolamine (TMAEEA),
trimethylaminopropylethanolamine (TMAPEA),
N-(2-cyanoethyl)ethylenediamine (CEEDA),
N-(2-cyanopropyl)ethylenediamine (CPEDA), and
ammonia (NH3).
10. The cleaning formulation according to claim 4 , further comprising at least one selected from the group consisting of:
an organic solvent,
a chelating agent,
a surfactant, and
phosphonic acid and/or phosphinic acid.
11. The cleaning formulation according to claim 10 , wherein 1-20% by weight of the organic solvent, 0.01-5% by weight of the chelating agent, 0.01-0.2% by weight of the surfactant, and 0.5-5% by weight of phosphonic acid and/or phosphinic acid are contained.
12. The cleaning formulation according to claim 10 , wherein the organic solvent is selected from the group consisting of:
1,4-butanediol (1,4-BD),
1,3-butanediol (1,3-BD),
ethylene glycol (EG),
propylene glycol (PG),
N-methylpyrrolidone (NMP),
γ-butyrolactone (GBL),
propylene glycol monomethylether (PGME), and
propylene glycol monomethylether acetate (PGMEA).
13. The cleaning formulation according to claim 10 , wherein the chelating agent is selected from the group consisting of:
ascorbic acid,
gluconic acid,
mannitol,
sorbitol, and
boric acid.
14. The cleaning formulation according to claim 10 , wherein the surfactant is a C1-10alkyl glucoside.
15. A method for cleaning a semiconductor wafer comprising:
cleaning the wafer by using a chemical formulation comprising an unsaturated dicarboxylic acid, and ethylene urea in semiconductor fabrication.
16. The method according to claim 15 , wherein the formulation is an aqueous solution.
17. The method according to claim 16 , wherein the formulation comprises
1-9% by weight of an unsaturated dicarboxylic acid; and
1-20% by weight of ethylene urea.
18. The method according to claim 16 , wherein the formulation further comprises:
at least one organic carboxylic acid except unsaturated dicarboxylic acid, and
at least one basic compound except ethylene urea.
19. The method according to claim 18 , wherein the formulation comprises:
1-9% by weight of an unsaturated dicarboxylic acid;
1-20% by weight of ethylene urea;
1-20% by weight of at least one organic carboxylic acid except unsaturated dicarboxylic acid;
0.1-50% by weight of at least one basic compound except ethylene urea; and
20-90% by weight of water.
20. The method according to claim 18 , wherein the unsaturated dicarboxylic acid is selected from the group consisting of maleic acid and citraconic acid.
21. The method according to claim 18 , wherein the unsaturated dicarboxylic acid is maleic acid.
22. The method according to claim 18 , wherein the organic carboxylic acid is selected from the group consisting of:
formic acid (FA),
acetic acid (AA), and
propionic acid (PA).
23. The method according to claim 18 , wherein the basic compound is selected from the group consisting of:
hydroxyethylpiperazine (HEP),
hydroxypropylpiperazine (HPP),
aminoethylpiperazine (AEP),
aminopropylpiperazine (APP),
hydroxyethylmorpholine (HEM),
hydroxypropylmorpholine (HPM),
aminoethylmorpholine (AEM),
aminopropylmorpholine (APM),
triethanolamine (TEA),
pentamethyldiethylenetriamine (PMDETA),
dimethylaminoethoxyethanol (DMAEE),
aminoethoxyethanol (AEE),
trimethylaminoethylethanolamine (TMAEEA),
trimethylaminopropylethanolamine (TMAPEA),
N-(2-cyanoethyl)ethylenediamine (CEEDA),
N-(2-cyanopropyl)ethylenediamine (CPEDA), and
ammonia (NH3).
24. The method according to claim 18 , wherein the formulation further comprises at least one selected from the group consisting of:
an organic solvent,
a chelating agent,
a surfactant, and
phosphonic acid and/or phosphinic acid.
25. The method according to claim 24 , wherein 1-20% by weight of the organic solvent, 0.01-5% by weight of the chelating agent, 0.01-0.2% by weight of the surfactant, and 0.5-5% by weight of phosphonic acid and/or phosphinic acid are contained.
26. The method according to claim 24 , wherein the organic solvent is selected from the group consisting of:
1,4-butanediol (1,4-BD),
1,3-butanediol (1,3-BD),
ethylene glycol (EG),
propylene glycol (PG),
N-methylpyrrolidone (NMP),
γ-butyrolactone (GBL),
propylene glycol monomethylether (PGME), and
propylene glycol monomethylether acetate (PGMEA).
27. The method according to claim 24 , wherein the chelating agent is selected from the group consisting of:
ascorbic acid,
gluconic acid,
mannitol,
sorbitol, and
boric acid.
28. The method according to claim 24 , wherein the surfactant is a C1-10alkyl glucoside.
29. A method for cleaning a semiconductor wafer comprising:
cleaning the wafer by using a chemical formulation comprising an unsaturated dicarboxylic acid, and ethylene urea, in a cleaning process after a following process:
(i) making via hole;
(ii) making trench;
(iii) punching of etch stopper layer; or
(iv) CMP (chemical mechanical polishing) process.
30. The method according to claim 29 , wherein the formulation is an aqueous solution.
31. The method according to claim 30 , wherein the formulation comprises
1-9% by weight of an unsaturated dicarboxylic acid; and
1-20% by weight of ethylene urea.
32. The method according to claim 30 , wherein the formulation further comprises:
at least one organic carboxylic acid except unsaturated dicarboxylic acid, and
at least one basic compound except ethylene urea.
33. The method according to claim 32 , wherein the formulation comprises:
1-9% by weight of an unsaturated dicarboxylic acid;
1-20% by weight of ethylene urea;
1-20% by weight of at least one organic carboxylic acid except unsaturated dicarboxylic acid;
0.1-50% by weight of at least one basic compound except ethylene urea; and
20-90% by weight of water.
34. The method according to claim 32 , wherein the unsaturated dicarboxylic acid is selected from the group consisting of maleic acid and citraconic acid.
35. The method according to claim 32 , wherein the unsaturated dicarboxylic acid is maleic acid.
36. The method according to claim 32 , wherein the organic carboxylic acid is selected from the group consisting of:
formic acid (FA),
acetic acid (AA), and
propionic acid (PA).
37. The method according to claim 32 , wherein the basic compound is selected from the group consisting of:
hydroxyethylpiperazine (HEP),
hydroxypropylpiperazine (HPP),
aminoethylpiperazine (AEP),
aminopropylpiperazine (APP),
hydroxyethylmorpholine (HEM),
hydroxypropylmorpholine (HPM),
aminoethylmorpholine (AEM),
aminopropylmorpholine (APM),
triethanolamine (TEA),
pentamethyldiethylenetriamine (PMDETA),
dimethylaminoethoxyethanol (DMAEE),
aminoethoxyethanol (AEE),
trimethylaminoethylethanolamine (TMAEEA),
trimethylaminopropylethanolamine (TMAPEA),
N-(2-cyanoethyl)ethylenediamine (CEEDA),
N-(2-cyanopropyl)ethylenediamine (CPEDA), and
ammonia (NH3).
38. The method according to claim 32 , wherein the formulation further comprises at least one selected from the group consisting of:
an organic solvent,
a chelating agent,
a surfactant, and
phosphonic acid and/or phosphinic acid.
39. The method according to claim 38 , wherein 1-20% by weight of the organic solvent, 0.01-5% by weight of the chelating agent, 0.01-0.2% by weight of the surfactant, and 0.5-5% by weight of phosphonic acid and/or phosphinic acid are contained.
40. The method according to claim 38 , wherein the organic solvent is selected from the group consisting of:
1,4-butanediol (1,4-BD),
1,3-butanediol (1,3-BD), ethylene glycol (EG),
propylene glycol (PG),
N-methylpyrrolidone (NMP),
γ-butyrolactone (GBL),
propylene glycol monomethylether (PGME), and
propylene glycol monomethylether acetate (PGMEA).
41. The method according to claim 38 , wherein the chelating agent is selected from the group consisting of:
ascorbic acid,
gluconic acid,
mannitol,
sorbitol, and
boric acid.
42. The method according to claim 38 , wherein the surfactant is a C1-10alkyl glucoside.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/577,481 US20070072782A1 (en) | 2003-10-30 | 2004-10-27 | Unsaturated dicarboxylic acid and ethylene urea containing formulation for cleaning semiconductor and cleaning method |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/695,773 US6946396B2 (en) | 2003-10-30 | 2003-10-30 | Maleic acid and ethylene urea containing formulation for removing residue from semiconductor substrate and method for cleaning wafer |
US10/695,773 | 2003-10-30 | ||
PCT/JP2004/015935 WO2005043610A1 (en) | 2003-10-30 | 2004-10-27 | Cleaning composition for semiconductor containing unsaturated dicarboxylic acid and ethylene urea and cleaning method |
US10/577,481 US20070072782A1 (en) | 2003-10-30 | 2004-10-27 | Unsaturated dicarboxylic acid and ethylene urea containing formulation for cleaning semiconductor and cleaning method |
Publications (1)
Publication Number | Publication Date |
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US20070072782A1 true US20070072782A1 (en) | 2007-03-29 |
Family
ID=34550005
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
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US10/695,773 Expired - Fee Related US6946396B2 (en) | 2003-10-30 | 2003-10-30 | Maleic acid and ethylene urea containing formulation for removing residue from semiconductor substrate and method for cleaning wafer |
US10/577,481 Abandoned US20070072782A1 (en) | 2003-10-30 | 2004-10-27 | Unsaturated dicarboxylic acid and ethylene urea containing formulation for cleaning semiconductor and cleaning method |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
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US10/695,773 Expired - Fee Related US6946396B2 (en) | 2003-10-30 | 2003-10-30 | Maleic acid and ethylene urea containing formulation for removing residue from semiconductor substrate and method for cleaning wafer |
Country Status (7)
Country | Link |
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US (2) | US6946396B2 (en) |
EP (1) | EP1684337A4 (en) |
JP (1) | JPWO2005043610A1 (en) |
KR (1) | KR20060096062A (en) |
CN (1) | CN100421222C (en) |
TW (1) | TW200524028A (en) |
WO (1) | WO2005043610A1 (en) |
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Also Published As
Publication number | Publication date |
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KR20060096062A (en) | 2006-09-05 |
JPWO2005043610A1 (en) | 2007-12-13 |
EP1684337A1 (en) | 2006-07-26 |
US20050096237A1 (en) | 2005-05-05 |
CN1875464A (en) | 2006-12-06 |
EP1684337A4 (en) | 2007-02-14 |
TW200524028A (en) | 2005-07-16 |
WO2005043610A1 (en) | 2005-05-12 |
US6946396B2 (en) | 2005-09-20 |
CN100421222C (en) | 2008-09-24 |
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