JPWO2006129549A1 - Cleaning liquid composition for semiconductor containing phosphonic acid and ascorbic acid and cleaning method - Google Patents
Cleaning liquid composition for semiconductor containing phosphonic acid and ascorbic acid and cleaning method Download PDFInfo
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- JPWO2006129549A1 JPWO2006129549A1 JP2007518938A JP2007518938A JPWO2006129549A1 JP WO2006129549 A1 JPWO2006129549 A1 JP WO2006129549A1 JP 2007518938 A JP2007518938 A JP 2007518938A JP 2007518938 A JP2007518938 A JP 2007518938A JP WO2006129549 A1 JPWO2006129549 A1 JP WO2006129549A1
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- semiconductor wafer
- cleaning
- ether
- composition
- component
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- 239000000203 mixture Substances 0.000 title claims abstract description 65
- 239000004065 semiconductor Substances 0.000 title claims abstract description 56
- 238000004140 cleaning Methods 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 41
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 title claims abstract description 27
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 229960005070 ascorbic acid Drugs 0.000 title claims abstract description 13
- 235000010323 ascorbic acid Nutrition 0.000 title claims abstract description 13
- 239000011668 ascorbic acid Substances 0.000 title claims abstract description 13
- 239000007788 liquid Substances 0.000 title abstract 2
- 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 abstract description 21
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 150000007514 bases Chemical class 0.000 claims abstract description 13
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- 125000003396 thiol group Chemical group [H]S* 0.000 claims abstract description 12
- 230000002378 acidificating effect Effects 0.000 claims abstract description 10
- 150000002222 fluorine compounds Chemical class 0.000 claims abstract description 9
- 238000012545 processing Methods 0.000 claims abstract description 8
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 14
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 11
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 10
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical group NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 10
- 235000019437 butane-1,3-diol Nutrition 0.000 claims description 10
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 10
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 10
- NSQSYCXRUVZPKI-UHFFFAOYSA-N 3-(2-aminoethylamino)propanenitrile Chemical compound NCCNCCC#N NSQSYCXRUVZPKI-UHFFFAOYSA-N 0.000 claims description 7
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 6
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 claims description 6
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 claims description 6
- 229940058015 1,3-butylene glycol Drugs 0.000 claims description 5
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 claims description 5
- JPIGSMKDJQPHJC-UHFFFAOYSA-N 1-(2-aminoethoxy)ethanol Chemical compound CC(O)OCCN JPIGSMKDJQPHJC-UHFFFAOYSA-N 0.000 claims description 5
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 5
- FENFUOGYJVOCRY-UHFFFAOYSA-N 1-propoxypropan-2-ol Chemical compound CCCOCC(C)O FENFUOGYJVOCRY-UHFFFAOYSA-N 0.000 claims description 5
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 claims description 5
- CUDYYMUUJHLCGZ-UHFFFAOYSA-N 2-(2-methoxypropoxy)propan-1-ol Chemical compound COC(C)COC(C)CO CUDYYMUUJHLCGZ-UHFFFAOYSA-N 0.000 claims description 5
- XYVAYAJYLWYJJN-UHFFFAOYSA-N 2-(2-propoxypropoxy)propan-1-ol Chemical compound CCCOC(C)COC(C)CO XYVAYAJYLWYJJN-UHFFFAOYSA-N 0.000 claims description 5
- KKFDCBRMNNSAAW-UHFFFAOYSA-N 2-(morpholin-4-yl)ethanol Chemical compound OCCN1CCOCC1 KKFDCBRMNNSAAW-UHFFFAOYSA-N 0.000 claims description 5
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 5
- YSAANLSYLSUVHB-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]ethanol Chemical compound CN(C)CCOCCO YSAANLSYLSUVHB-UHFFFAOYSA-N 0.000 claims description 5
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 5
- FLFWJIBUZQARMD-UHFFFAOYSA-N 2-mercapto-1,3-benzoxazole Chemical compound C1=CC=C2OC(S)=NC2=C1 FLFWJIBUZQARMD-UHFFFAOYSA-N 0.000 claims description 5
- WFCSWCVEJLETKA-UHFFFAOYSA-N 2-piperazin-1-ylethanol Chemical compound OCCN1CCNCC1 WFCSWCVEJLETKA-UHFFFAOYSA-N 0.000 claims description 5
- HWJSDSLWRKEWOL-UHFFFAOYSA-N 3-(2-aminoethylamino)-2-methylpropanenitrile Chemical compound N#CC(C)CNCCN HWJSDSLWRKEWOL-UHFFFAOYSA-N 0.000 claims description 5
- MEQHCCFDNHLMRV-UHFFFAOYSA-N 3-(3-aminopropylamino)propanenitrile Chemical compound NCCCNCCC#N MEQHCCFDNHLMRV-UHFFFAOYSA-N 0.000 claims description 5
- VHEATSVPRJFWMU-UHFFFAOYSA-N 3-[2-aminoethyl(methyl)amino]propanenitrile Chemical compound NCCN(C)CCC#N VHEATSVPRJFWMU-UHFFFAOYSA-N 0.000 claims description 5
- NPMCIHCQSNHBDX-UHFFFAOYSA-N 3-[2-cyanoethyl(methyl)amino]propanenitrile Chemical compound N#CCCN(C)CCC#N NPMCIHCQSNHBDX-UHFFFAOYSA-N 0.000 claims description 5
- UIKUBYKUYUSRSM-UHFFFAOYSA-N 3-morpholinopropylamine Chemical compound NCCCN1CCOCC1 UIKUBYKUYUSRSM-UHFFFAOYSA-N 0.000 claims description 5
- VATRWWPJWVCZTA-UHFFFAOYSA-N 3-oxo-n-[2-(trifluoromethyl)phenyl]butanamide Chemical compound CC(=O)CC(=O)NC1=CC=CC=C1C(F)(F)F VATRWWPJWVCZTA-UHFFFAOYSA-N 0.000 claims description 5
- UVLSCMIEPPWCHZ-UHFFFAOYSA-N 3-piperazin-1-ylpropan-1-amine Chemical compound NCCCN1CCNCC1 UVLSCMIEPPWCHZ-UHFFFAOYSA-N 0.000 claims description 5
- 229920001174 Diethylhydroxylamine Polymers 0.000 claims description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 5
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 claims description 5
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 claims description 5
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 claims description 5
- 235000011187 glycerol Nutrition 0.000 claims description 5
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical compound O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 claims description 5
- YPEWWOUWRRQBAX-UHFFFAOYSA-N n,n-dimethyl-3-oxobutanamide Chemical compound CN(C)C(=O)CC(C)=O YPEWWOUWRRQBAX-UHFFFAOYSA-N 0.000 claims description 5
- RWIVICVCHVMHMU-UHFFFAOYSA-N n-aminoethylmorpholine Chemical compound NCCN1CCOCC1 RWIVICVCHVMHMU-UHFFFAOYSA-N 0.000 claims description 5
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 5
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 5
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 claims description 4
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 claims description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- QHJABUZHRJTCAR-UHFFFAOYSA-N n'-methylpropane-1,3-diamine Chemical compound CNCCCN QHJABUZHRJTCAR-UHFFFAOYSA-N 0.000 claims 2
- 239000006187 pill Substances 0.000 claims 1
- CIWBSHSKHKDKBQ-MVHIGOERSA-N D-ascorbic acid Chemical compound OC[C@@H](O)[C@@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-MVHIGOERSA-N 0.000 abstract 1
- 239000010949 copper Substances 0.000 description 15
- 239000000126 substance Substances 0.000 description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 13
- 229910052802 copper Inorganic materials 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 239000011229 interlayer Substances 0.000 description 8
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 7
- 239000005751 Copper oxide Substances 0.000 description 7
- 229910000431 copper oxide Inorganic materials 0.000 description 7
- 238000005260 corrosion Methods 0.000 description 7
- 230000007797 corrosion Effects 0.000 description 7
- 238000004380 ashing Methods 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 229910017855 NH 4 F Inorganic materials 0.000 description 2
- QQQCWVDPMPFUGF-ZDUSSCGKSA-N alpinetin Chemical compound C1([C@H]2OC=3C=C(O)C=C(C=3C(=O)C2)OC)=CC=CC=C1 QQQCWVDPMPFUGF-ZDUSSCGKSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- 238000001312 dry etching Methods 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
- 238000000206 photolithography Methods 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- 229910021594 Copper(II) fluoride Inorganic materials 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- 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 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- GWFAVIIMQDUCRA-UHFFFAOYSA-L copper(ii) fluoride Chemical compound [F-].[F-].[Cu+2] GWFAVIIMQDUCRA-UHFFFAOYSA-L 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
- H01L21/02068—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers
- H01L21/02071—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers the processing being a delineation, e.g. RIE, of conductive layers
-
- 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
- C11D7/08—Acids
-
- 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
- C11D7/26—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
- C11D7/34—Organic compounds containing sulfur
-
- 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
-
- 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
- G03F7/426—Stripping or agents therefor using liquids only containing organic halogen compounds; containing organic sulfonic acids or salts thereof; containing sulfoxides
-
- C11D2111/22—
Abstract
【課題】ホスホン酸及びアスコルビン酸を含む半導体用洗浄液組成物及び洗浄方法を提供すること。【解決手段】本発明は、半導体ウェハ加工工程において、残渣物を洗浄するための組成物及び洗浄方法に関する。前記組成物は、（a）フッ化水素酸、酸性フッ化アンモニウム及びフッ化アンモニウムから選択される少なくとも１種のフッ素化合物、（ｂ）少なくとも１種の有機溶媒、（ｃ）ホスホン酸、（ｄ）アスコルビン酸、（ｅ）少なくとも１種の塩基性化合物、及び（ｆ）水を含有する。また、この組成物に任意成分として、（ｇ）少なくとも１種のメルカプト基を有する防食剤を加えてもよい。【選択図】なしDisclosed is a semiconductor cleaning liquid composition containing phosphonic acid and ascorbic acid, and a cleaning method. The present invention relates to a composition and a cleaning method for cleaning residues in a semiconductor wafer processing step. The composition comprises (a) at least one fluorine compound selected from hydrofluoric acid, acidic ammonium fluoride and ammonium fluoride, (b) at least one organic solvent, (c) phosphonic acid, (d Ascorbic acid), (e) at least one basic compound, and (f) water. Moreover, you may add the anticorrosive which has (g) at least 1 sort (s) of mercapto group as an arbitrary component to this composition. [Selection figure] None
Description
本発明は概して、半導体ウェハの加工に用いられる化学組成物、特に、半導体基板上に銅及び銅合金を主成分とする金属配線を形成する過程に生じる残渣を除去し得る化学組成物に関する。 The present invention generally relates to a chemical composition used for processing a semiconductor wafer, and more particularly to a chemical composition capable of removing residues generated in the process of forming a metal wiring mainly composed of copper and a copper alloy on a semiconductor substrate.
半導体素子は、通常、基板上に形成された配線材料となる金属膜や層間絶縁膜となる絶縁材料上にレジスト膜を塗布し、フォトリソグラフィー工程・ドライエッチング工程を経て製造される。フォトリソグラフィー工程後に残存するレジスト膜はプラズマアッシング工程により除去され、ドライエッチング工程及びプラズマアッシング工程により生じる配線材料や層間絶縁膜材料上に残存する残渣は、一般的に、ウェット処理によって、即ち、化学組成物によって除去される。 A semiconductor element is usually manufactured through a photolithography process and a dry etching process by applying a resist film on a metal film that is a wiring material formed on a substrate and an insulating material that is an interlayer insulating film. The resist film remaining after the photolithography process is removed by the plasma ashing process, and the residue remaining on the wiring material and the interlayer insulating film material generated by the dry etching process and the plasma ashing process is generally performed by wet processing, that is, by chemical treatment. Removed by the composition.
従来配線材料には、アルミニウム及びアルミニウム合金が使用されており、その際の化学組成物としては、アルカリ性アミン系のもの（例えば、特許文献１参照。）、フッ素化合物系のもの（例えば、特許文献２参照。）及び有機カルボン酸系のもの（例えば、特許文献３参照。）が報告されている。
しかしながら近年では、半導体素子の微細化、高速化の要求に伴い、配線材料は従来のアルミニウム合金からより低い抵抗率を有する銅に、層間絶縁膜はより低い誘電率を有するいわゆるｌｏｗ−ｋ材料への移行が急速に進行しており、従来の化学組成物では、銅などの配線金属やｌｏｗ−ｋ材料を不必要に除去してしまうという問題があった。そのため、レジストアッシング後の工程において効率よく残渣を除去し、かつ配線金属やｌｏｗ−ｋ材料へ影響を及ぼさない化学組成物が必要とされている。
一方、銅配線やｌｏｗ−ｋ材料向けの化学組成物としては、フッ化水素酸の塩とホスホン酸等を用いた化学組成物（特開２００４−９４２０３号公報）が報告されている。However, in recent years, with the demand for miniaturization and higher speed of semiconductor elements, the wiring material is changed from a conventional aluminum alloy to copper having a lower resistivity, and the interlayer insulating film is changed to a so-called low-k material having a lower dielectric constant. The conventional chemical composition has a problem that it unnecessarily removes a wiring metal such as copper and a low-k material. Therefore, there is a need for a chemical composition that efficiently removes residues in the process after resist ashing and does not affect the wiring metal or low-k material.
On the other hand, as a chemical composition for copper wiring and low-k materials, a chemical composition using a salt of hydrofluoric acid and phosphonic acid (Japanese Patent Laid-Open No. 2004-94203) has been reported.
本発明者は、上記の課題を解決するために鋭意研究を重ねた結果、銅配線及びｌｏｗ−ｋ材料を腐食することなく、効率よく残渣を除去することが可能な化学組成物及びこれを用いた半導体洗浄方法を見い出した。 As a result of intensive studies to solve the above problems, the present inventor has used a chemical composition capable of efficiently removing a residue without corroding copper wiring and low-k material, and the use of the chemical composition. Found a semiconductor cleaning method.
即ち、本発明は以下の態様に関する：
（１）半導体ウェハ加工工程に使用される、
（ａ）フッ化水素酸、酸性フッ化アンモニウム及びフッ化アンモニウムからなる群から選択される少なくとも１種のフッ素化合物、
（ｂ）少なくとも１種の有機溶媒、
（ｃ）ホスホン酸、
（ｄ）アスコルビン酸、
（ｅ）少なくとも１種の塩基性化合物、及び
（ｆ）水
を含む半導体ウェハ洗浄用組成物；
（２）前記組成物の成分（ａ）〜成分（ｆ）の各濃度が以下の質量％で表され、かつ各成分濃度の合計が１００％となる、（１）に記載の半導体ウェハ洗浄用組成物。
（４）前記（ｃ）ホスホン酸の成分濃度が前記（ｄ）アスコルビン酸の成分濃度よりも低いことを特徴とする（２）に記載の半導体ウェハ洗浄用組成物；
（５）前記（ｅ）少なくとも１種の塩基性化合物が、トリエタノールアミン、アミノエトキシエタノール、ヒドロキシエチルモルホリン、ヒドロキシエチルピペラジン、アミノエチルモルホリン、アミノエチルピペラジン、アミノプロピルモルホリン、アミノプロピルピペラジン、ペンタメチルジエチレントリアミン、ジメチルアミノエトキシエタノール、トリメチルアミノエチルエタノールアミン、トリメチルアミノプロピルエタノールアミン、Ｎ−（２−シアノエチル）エチレンジアミン、Ｎ−（２−シアノプロピル）エチレンジアミン、アンモニア、テトラメチルアンモニウム水酸化物、エチレン尿素、Ｎ−（２−シアノエチル）−Ｎ−メチルエチレンジアミン、Ｎ−（２−シアノエチル）トリメチレンジアミン、Ｎ−（２−シアノエチル）−Ｎ−メチルトリメチレンジアミン、ビス（２−シアノエチル）メチルアミン、及びＮ，Ｎ−ジエチルヒドロキシルアミンからなる群から選択される（１）に記載の半導体ウェハ洗浄用組成物；
（６）更に、（ｇ）メルカプト基を有する少なくとも１種の防食剤を含む（１）に記載の半導体ウェハ洗浄用組成物；
（７）前記組成物の成分（ａ）〜成分（ｇ）の各濃度が以下の質量％で表され、かつ各成分濃度の合計が１００％となる、（１）に記載の半導体ウェハ洗浄用組成物。
ールからなる群から選択される（６）に記載の半導体ウェハ洗浄用組成物；
（９）半導体ウェハ加工工程において、
（ａ）フッ化水素酸、酸性フッ化アンモニウム及びフッ化アンモニウムからなる群から選択される少なくとも１種のフッ素化合物、
（ｂ）少なくとも１種の有機溶媒、
（ｃ）ホスホン酸、
（ｄ）アスコルビン酸、
（ｅ）少なくとも１種の塩基性化合物、及び
（ｆ）水
を含む半導体ウェハ洗浄用組成物を使用することによる半導体ウェハの洗浄方法；
（１０）前記半導体ウェハ洗浄用組成物の成分（ａ）〜成分（ｆ）の各濃度が以下の質量％で表され、かつ各成分濃度の合計が１００％となる、（９）に記載の半導体ウェハの洗浄方法。
（１２）前記（ｃ）ホスホン酸の成分濃度が前記（ｄ）アスコルビン酸の成分濃度よりも低いことを特徴とする（１０）に記載の半導体ウェハの洗浄方法；
（１３）前記（ｅ）少なくとも１種の塩基性化合物が、トリエタノールアミン、アミノエトキシエタノール、ヒドロキシエチルモルホリン、ヒドロキシエチルピペラジン、アミノエチルモルホリン、アミノエチルピペラジン、アミノプロピルモルホリン、アミノプロピルピペラジン、ペンタメチルジエチレントリアミン、ジメチルアミノエトキシエタノール、トリメチルアミノエチルエタノールアミン、トリメチルアミノプロピルエタノールアミン、Ｎ−（２−シアノエチル）エチレンジアミン、Ｎ−（２−シアノプロピル）エチレンジアミン、アンモニア、テトラメチルアンモニウム水酸化物、エチレン尿素、Ｎ−（２−シアノエチル）−Ｎ−メチルエチレンジアミン、Ｎ−（２−シアノエチル）トリメチレンジアミン、Ｎ−（２−シアノエチル）−Ｎ−メチルトリメチレンジアミン、ビス（２−シアノエチル）メチルアミン、及びＮ，Ｎ−ジエチルヒドロキシルアミンからなる群から選択される（９）に記載の半導体ウェハの洗浄方法；
（１４）前記半導体ウェハ洗浄用組成物が、更に、（ｇ）メルカプト基を有する少なくとも１種の防食剤を含む（９）に記載の半導体ウェハの洗浄方法；
（１５）前記半導体ウェハ洗浄用組成物の成分（ａ）〜成分（ｇ）の各濃度が以下の質量％で表され、かつ各成分濃度の合計が１００％となる、（９）に記載の半導体ウェハの洗浄方法。
(1) Used in semiconductor wafer processing process
(A) at least one fluorine compound selected from the group consisting of hydrofluoric acid, acidic ammonium fluoride and ammonium fluoride,
(B) at least one organic solvent,
(C) phosphonic acid,
(D) ascorbic acid,
(E) a semiconductor wafer cleaning composition comprising at least one basic compound, and (f) water;
(2) The semiconductor wafer cleaning according to (1), wherein each concentration of the component (a) to the component (f) of the composition is represented by the following mass%, and the total concentration of each component is 100%. Composition.
(4) The composition for cleaning a semiconductor wafer according to (2), wherein the component concentration of (c) phosphonic acid is lower than the component concentration of (d) ascorbic acid;
(5) The (e) at least one basic compound is triethanolamine, aminoethoxyethanol, hydroxyethylmorpholine, hydroxyethylpiperazine, aminoethylmorpholine, aminoethylpiperazine, aminopropylmorpholine, aminopropylpiperazine, pentamethyl Diethylenetriamine, dimethylaminoethoxyethanol, trimethylaminoethylethanolamine, trimethylaminopropylethanolamine, N- (2-cyanoethyl) ethylenediamine, N- (2-cyanopropyl) ethylenediamine, ammonia, tetramethylammonium hydroxide, ethyleneurea, N- (2-cyanoethyl) -N-methylethylenediamine, N- (2-cyanoethyl) trimethylenediamine, N- (2-cyanoethyl) Le) -N- methyltrimethylene diamine, bis (2-cyanoethyl) methylamine, and N, the semiconductor wafer cleaning composition according to selected from the group consisting of N- diethylhydroxylamine (1);
(6) The semiconductor wafer cleaning composition according to (1), further comprising (g) at least one anticorrosive having a mercapto group;
(7) The semiconductor wafer cleaning according to (1), wherein each concentration of the component (a) to the component (g) of the composition is represented by the following mass%, and the total concentration of each component is 100%. Composition.
(9) In the semiconductor wafer processing process,
(A) at least one fluorine compound selected from the group consisting of hydrofluoric acid, acidic ammonium fluoride and ammonium fluoride,
(B) at least one organic solvent,
(C) phosphonic acid,
(D) ascorbic acid,
(E) a method of cleaning a semiconductor wafer by using a composition for cleaning a semiconductor wafer comprising at least one basic compound and (f) water;
(10) The concentration of each of the components (a) to (f) of the semiconductor wafer cleaning composition is represented by the following mass%, and the total concentration of each component is 100%, Semiconductor wafer cleaning method.
(12) The method for cleaning a semiconductor wafer according to (10), wherein the component concentration of (c) phosphonic acid is lower than the component concentration of (d) ascorbic acid;
(13) (e) at least one basic compound is triethanolamine, aminoethoxyethanol, hydroxyethylmorpholine, hydroxyethylpiperazine, aminoethylmorpholine, aminoethylpiperazine, aminopropylmorpholine, aminopropylpiperazine, pentamethyl Diethylenetriamine, dimethylaminoethoxyethanol, trimethylaminoethylethanolamine, trimethylaminopropylethanolamine, N- (2-cyanoethyl) ethylenediamine, N- (2-cyanopropyl) ethylenediamine, ammonia, tetramethylammonium hydroxide, ethyleneurea, N- (2-cyanoethyl) -N-methylethylenediamine, N- (2-cyanoethyl) trimethylenediamine, N- (2-cyano Chill) -N- methyltrimethylene diamine, bis (2-cyanoethyl) methylamine, and N, the method of cleaning a semiconductor wafer according to selected from the group consisting of N- diethylhydroxylamine (9);
(14) The method for cleaning a semiconductor wafer according to (9), wherein the composition for cleaning a semiconductor wafer further comprises (g) at least one anticorrosive having a mercapto group;
(15) Each concentration of the component (a) to the component (g) of the semiconductor wafer cleaning composition is represented by the following mass%, and the total of the component concentrations is 100%, according to (9) Semiconductor wafer cleaning method.
本発明の半導体ウェハ洗浄用組成物は、従来のアミン系、フッ化アンモニウム系洗浄液に比べてｌｏｗ−ｋ材料、更にはｕｌｔｒａ ｌｏｗ−ｋ材料、銅、アルミニウム、アルミニウム合金に対する腐食性が極めて低く、効率よく、プラズマアッシング工程後の残渣、プラズマアッシング工程後のエッチストッパ層のエッチング残渣、プラズマアッシング工程後の酸化銅等の金属酸化物及びフッ化銅等の金属ハロゲン化物、及びＣＭＰ（化学的機械的研磨）後の酸化銅等の金属酸化物を除去できるという効果を有する。 The semiconductor wafer cleaning composition of the present invention has extremely low corrosiveness to low-k materials, ultra low-k materials, copper, aluminum, and aluminum alloys as compared to conventional amine-based and ammonium fluoride-based cleaning solutions. Efficiently, the residue after the plasma ashing process, the etching residue of the etch stopper layer after the plasma ashing process, the metal oxide such as copper oxide and the metal halide such as copper fluoride after the plasma ashing process, and CMP (chemical machine) This has the effect of removing metal oxides such as copper oxide after mechanical polishing.
本発明の上記及びその他の特徴および利点は、好ましい実施態様の以下の詳細な説明により当業者に容易に理解され得るものである。 These and other features and advantages of the present invention will be readily apparent to those skilled in the art from the following detailed description of preferred embodiments.
本発明は、半導体ウェハを、高密度プラズマによりエッチング及びアッシングした際に生じる残渣を除去するのに適した化学組成物であり、（ａ）フッ化水素酸、酸性フッ化アンモニウム及びフッ化アンモニウムからなる群から選択される少なくとも１種のフッ素化合物、（ｂ）少なくとも１種の有機溶媒、（ｃ）ホスホン酸、（ｄ）アスコルビン酸、（ｅ）少なくとも１種の塩基性化合物、及び（ｆ）水を含有する。また、この組成物に任意成分として、（ｇ）少なくとも１種のメルカプト基を有する防食剤を加えてもよい。
また、当該化学組成物のｐＨは、３−１０が好ましく、より好ましくは４−８である。The present invention is a chemical composition suitable for removing residues generated when a semiconductor wafer is etched and ashed by high-density plasma, and comprises (a) hydrofluoric acid, acidic ammonium fluoride, and ammonium fluoride. At least one fluorine compound selected from the group consisting of: (b) at least one organic solvent, (c) phosphonic acid, (d) ascorbic acid, (e) at least one basic compound, and (f) Contains water. Moreover, you may add the anticorrosive which has (g) at least 1 sort (s) of mercapto group as an arbitrary component to this composition.
Moreover, 3-10 are preferable and, as for pH of the said chemical composition, More preferably, it is 4-8.
前記（ａ）フッ化水素酸、酸性フッ化アンモニウム及びフッ化アンモニウムからなる群から選択される少なくとも１種のフッ素化合物は、好ましくは、酸性フッ化アンモニウム及びフッ化アンモニウムから選択される。
前記（ａ）フッ化水素酸、酸性フッ化アンモニウム及びフッ化アンモニウムからなる群から選択される少なくとも１種のフッ素化合物の成分濃度は、全成分の濃度に基づき、０．５−５質量％が好ましく、より好ましくは０．８−２．５質量％である。The (a) at least one fluorine compound selected from the group consisting of hydrofluoric acid, acidic ammonium fluoride, and ammonium fluoride is preferably selected from acidic ammonium fluoride and ammonium fluoride.
The component concentration of at least one fluorine compound selected from the group consisting of (a) hydrofluoric acid, acidic ammonium fluoride, and ammonium fluoride is 0.5-5% by mass based on the concentration of all components. Preferably, it is 0.8-2.5 mass%.
前記（ｂ）少なくとも１種の有機溶媒は、好ましくは、ホルムアミド、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ，Ｎ−ジメチルアセトアセトアミド、Ｎ−メチルピロリドン、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、１，３−ブチレングリコール、プロピレングリコールモノメチルエーテル、プロピレングリコールｎ−プロピルエーテル、ジプロピレングリコールメチルエーテル、ジプロピレングリコールｎ−プロピルエーテル、ジプロピレングリコールジメチルエーテル、トリプロピレングリコールｎ−プロピルエーテル、グリセリン、エチレンカーボネート、プロピレンカーボネート、スルホラン、１，３−ブタンジオール、１，４−ブタンジオール、及びγ−ブチロラクトンからなる群から選択され、これらを２種以上組み合わせて使用してもよい。
また、グリコールエーテル系溶媒と他の有機溶媒との併用が好ましく、層間絶縁膜への濡れ性、残渣除去性を向上させることが可能となる。
特に好ましいグリコールエーテル系溶媒としては、エチレングリコールモノブチルエーテルが挙げられる。
また前記（ｂ）少なくとも１種の有機溶媒の成分濃度は、全成分の濃度に基づき、１０−７０質量％が好ましく、より好ましくは２０−６０質量％である。The (b) at least one organic solvent is preferably formamide, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylacetoacetamide, N-methylpyrrolidone, ethylene glycol monomethyl ether, ethylene Glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, 1,3-butylene glycol, propylene glycol monomethyl ether, propylene glycol n-propyl ether, dipropylene glycol methyl ether, dipropylene Glycol n-propyl ether, dipropylene glycol dimethyl ether, tripropylene glycol N-propyl ether, glycerin, ethylene carbonate, propylene carbonate, sulfolane, 1,3-butanediol, 1,4-butanediol, and γ-butyrolactone are used in combination of two or more. May be.
In addition, it is preferable to use a glycol ether solvent in combination with another organic solvent, and the wettability to the interlayer insulating film and the residue removal property can be improved.
A particularly preferred glycol ether solvent is ethylene glycol monobutyl ether.
The component concentration of the (b) at least one organic solvent is preferably 10-70% by mass, more preferably 20-60% by mass, based on the concentration of all components.
前記（ｃ）ホスホン酸の成分濃度は、全成分の濃度に基づき、０．１−５質量％が好ましく、より好ましくは０．５−３質量％である。 The component concentration of (c) phosphonic acid is preferably 0.1-5 mass%, more preferably 0.5-3 mass%, based on the concentration of all components.
前記（ｄ）アスコルビン酸の成分濃度は、全成分の濃度に基づき、１−１０質量％が好ましく、より好ましくは３−７質量％である。 The component concentration of (d) ascorbic acid is preferably 1-10% by mass, more preferably 3-7% by mass, based on the concentration of all components.
また、（ｃ）ホスホン酸の成分濃度は（ｄ）アスコルビン酸の成分濃度より低いことが好ましい。 Further, the component concentration of (c) phosphonic acid is preferably lower than the component concentration of (d) ascorbic acid.
前記（ｅ）少なくとも１種の塩基性化合物は、好ましくは、トリエタノールアミン、アミノエトキシエタノール、ヒドロキシエチルモルホリン、ヒドロキシエチルピペラジン、アミノエチルモルホリン、アミノエチルピペラジン、アミノプロピルモルホリン、アミノプロピルピペラジン、ペンタメチルジエチレントリアミン、ジメチルアミノエトキシエタノール、トリメチルアミノエチルエタノールアミン、トリメチルアミノプロピルエタノールアミン、Ｎ−（２−シアノエチル）エチレンジアミン、Ｎ−（２−シアノプロピル）エチレンジアミン、アンモニア、テトラメチルアンモニウム水酸化物、エチレン尿素、Ｎ−（２−シアノエチル）−Ｎ−メチルエチレンジアミン、Ｎ−（２−シアノエチル）トリメチレンジアミン、Ｎ−（２−シアノエチル）−Ｎ−メチルトリメチレンジアミン、ビス（２−シアノエチル）メチルアミン、及びＮ，Ｎ−ジエチルヒドロキシルアミンからなる群から選択され、これらを２種以上組み合わせて使用してもよい。
さらに好ましくは、前記（ｅ）少なくとも１種の塩基性化合物は、Ｎ−（２−シアノエチル）エチレンジアミン、及びアンモニアからなる群から選択され、これらを組み合わせて使用してもよい。
前記（ｅ）少なくとも１種の塩基性化合物の成分濃度は、全成分の濃度に基づき、０．５−１５質量％が好ましく、より好ましくは５−１５質量％である。The (e) at least one basic compound is preferably triethanolamine, aminoethoxyethanol, hydroxyethylmorpholine, hydroxyethylpiperazine, aminoethylmorpholine, aminoethylpiperazine, aminopropylmorpholine, aminopropylpiperazine, pentamethyl. Diethylenetriamine, dimethylaminoethoxyethanol, trimethylaminoethylethanolamine, trimethylaminopropylethanolamine, N- (2-cyanoethyl) ethylenediamine, N- (2-cyanopropyl) ethylenediamine, ammonia, tetramethylammonium hydroxide, ethyleneurea, N- (2-cyanoethyl) -N-methylethylenediamine, N- (2-cyanoethyl) trimethylenediamine, N- (2-si Aminoethyl) -N- methyltrimethylene diamine, bis (2-cyanoethyl) methylamine, and N, is selected from the group consisting of N- diethylhydroxylamine, it may be used in combination of two or more of these.
More preferably, the (e) at least one basic compound is selected from the group consisting of N- (2-cyanoethyl) ethylenediamine and ammonia, and these may be used in combination.
The component concentration of the (e) at least one basic compound is preferably 0.5-15% by mass, more preferably 5-15% by mass, based on the concentration of all components.
前記（ｆ）水の成分濃度は、全成分の濃度に基づき、２０−５０質量％が好ましい。 The component concentration of water (f) is preferably 20-50% by mass based on the concentration of all components.
前記（ｇ）メルカプト基を有する少なくとも１種の防食剤は、好ましくは、２−メルカプトベンゾキサゾール、２−メルカプトベンゾイミダゾール、及び２−メルカプトベンゾテトラゾールからなる群から選択される。
前記（ｇ）メルカプト基を有する少なくとも１種の防食剤の成分濃度は、全成分の濃度に基づき、０．００１−０．０５質量％が好ましく、より好ましくは０．００５−０．０３質量％である。The (g) at least one anticorrosive having a mercapto group is preferably selected from the group consisting of 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, and 2-mercaptobenzotetrazole.
The component concentration of the (g) at least one anticorrosive having a mercapto group is preferably 0.001-0.05% by mass, more preferably 0.005-0.03% by mass, based on the concentration of all components. It is.
当該組成物の使用温度は、残渣物が完全に除去できる範囲の温度であれば限定されないが、例えば２１〜４０℃の低温で十分な効果が得られる。 Although the use temperature of the said composition will not be limited if it is the temperature of the range which can remove a residue completely, For example, sufficient effect is acquired at the low temperature of 21-40 degreeC.
当該組成物の使用時間は、残渣物が完全に除去できる範囲の時間であれば限定されないが、例えば１〜５分の短時間で十分な効果が得られる。 Although the usage time of the said composition will not be limited if it is the time of the range which can remove a residue completely, For example, sufficient effect is acquired in 1 to 5 minutes for a short time.
当該組成物の使用方法は、当該組成物が残渣物を含む半導体ウェハに接触していれば、
特に限定されないが、バッチ式、枚葉式洗浄装置での使用が好ましい。If the composition is in contact with a semiconductor wafer containing residues,
Although it does not specifically limit, Use with a batch type and a single wafer type washing | cleaning apparatus is preferable.
また、当該組成物は、半導体ウェハ加工工程のうちウェハに残渣物が存在するあらゆる工程において使用され得るが、例えば、そしてまた好適なものとして、（１）ビア孔の形成後の洗浄工程、（２）配線溝の形成後の洗浄工程、（３）エッチストッパ膜のパンチング後の洗浄工程、（４）ＣＭＰ（化学的機械的研磨）後の洗浄工程において使用可能である。 In addition, the composition can be used in any process of semiconductor wafer processing where residues are present on the wafer. For example, and preferably, (1) a cleaning process after formation of via holes, ( It can be used in 2) a cleaning process after the formation of the wiring trench, (3) a cleaning process after punching of the etch stopper film, and (4) a cleaning process after CMP (chemical mechanical polishing).
以下に実施例を挙げて本発明を説明するが、本発明はこれらに限定されるものではない。
（１）銅酸化物の除去性評価試験
銅が成膜されたウェハを、酸素プラズマ（２５０℃、１２０秒間）処理し、銅膜を強制的に酸化させ、得られた銅酸化物を評価に用いた。これを実施例１〜４の組成物に２５℃、１０分間浸漬し、ウェハを水洗、風乾した。
銅酸化物の除去性評価は、光学顕微鏡による目視的観察及びＸ線光電子分光分析法［ＸＰＳ：島津製作所製ＥＳＣＡ３２００］によるウェハ表面上のＣｕ価数の定性分析により総合的に判断した。
実施例１〜４の組成物の各組成及び実験結果を表１に示す。なお銅酸化物除去性は以下にように評価した。
○：光学顕微鏡で黄色、かつＸＰＳ測定でＣｕ２＋ピーク検出されず。
△：光学顕微鏡で黄色、かつＸＰＳ測定でＣｕ２＋ピーク検出。
×：光学顕微鏡で赤銅色、かつＸＰＳ測定でＣｕ２＋ピークを検出。Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited thereto.
(1) Copper oxide removability evaluation test A copper-formed wafer was treated with oxygen plasma (250 ° C., 120 seconds) to forcibly oxidize the copper film, and the obtained copper oxide was evaluated. Using. This was immersed in the compositions of Examples 1 to 4 at 25 ° C. for 10 minutes, and the wafer was washed with water and air dried.
The removal evaluation of the copper oxide was comprehensively judged by visual observation with an optical microscope and qualitative analysis of the Cu valence on the wafer surface by X-ray photoelectron spectroscopy [XPS: ESCA3200 manufactured by Shimadzu Corporation].
Table 1 shows the compositions and experimental results of the compositions of Examples 1 to 4. The copper oxide removability was evaluated as follows.
○: Yellow with an optical microscope and no Cu 2+ peak detected by XPS measurement.
(Triangle | delta): Yellow with an optical microscope and Cu2 + peak detection by XPS measurement.
X: Bronze color with an optical microscope, and Cu 2+ peak detected with XPS measurement.
（２）銅配線への耐腐食性評価試験
銅配線への耐腐食性には銅板チップ（膜厚１６５０ｎｍ、３ｃm×３ｃm）を用いた。これらのチップを実施例１〜４の組成物に２５℃、１０分間浸漬し、チップを水洗、風乾した際の銅チップのエッチング量（膜厚の減少量）を４端子法によるシート抵抗測定装置（国際電気α社製ＶＲ‐１２０）によって測定した。
実施例１〜４の組成物の各組成及び実験結果を表１に示す。なお銅配線への耐腐食性は以下のように評価した。
○：膜厚減少が２ｎｍ未満。
×：膜厚減少が２ｎｍ以上。(2) Corrosion resistance evaluation test for copper wiring A copper plate chip (film thickness 1650 nm, 3 cm × 3 cm) was used for the corrosion resistance to the copper wiring. A sheet resistance measuring device using a four-terminal method to measure the etching amount (thickness reduction) of the copper chip when these chips were immersed in the compositions of Examples 1 to 4 at 25 ° C. for 10 minutes, washed with water, and air-dried. It was measured by (VR-120 manufactured by Kokusai Electric α Co.).
Table 1 shows the compositions and experimental results of the compositions of Examples 1 to 4. The corrosion resistance to the copper wiring was evaluated as follows.
○: Reduction in film thickness is less than 2 nm.
X: Film thickness reduction is 2 nm or more.
（３）層間絶縁膜（ｌｏｗ−ｋ膜）への耐腐食性評価試験
ｌｏｗ−ｋ膜への耐腐食性にはＣＶＤ−ＳｉＯＣ膜チップ（膜厚５００ｎｍ、３ｃｍ×３ｃm、ｋ値２．５）を用いた。このチップを実施例１〜３の組成物に２５℃、１０分間浸漬し、チップを水洗、風乾した際のＣＶＤ−ＳｉＯＣ膜のエッチング量（膜厚の減少量）を分光エリプソメーター（ｎ＆ｋ社製ｎ＆ｋ ａｎａｌｙｓｉｓｅｒ）によって測定した。
実施例１〜４の組成物の各組成及び実験結果を表１に示す。なおｌｏｗ−ｋ膜への耐腐食性は以下のように評価した。
○：膜厚減少率が０．１ｎｍ／分未満かつ屈折率変化が０．０１未満。
×：膜厚減少率が０．１ｎｍ／分以上及び／又は屈折率変化が０．０１以上。(3) Corrosion resistance evaluation test for interlayer insulating film (low-k film) CVD-SiOC film chip (film thickness 500 nm, 3 cm × 3 cm, k value 2.5) for corrosion resistance to low-k film Was used. This chip was immersed in the composition of Examples 1 to 3 at 25 ° C. for 10 minutes, and the etching amount (thickness reduction amount) of the CVD-SiOC film when the chip was washed with water and air dried was measured by a spectroscopic ellipsometer (manufactured by n & k). n & k analyzer).
Table 1 shows the compositions and experimental results of the compositions of Examples 1 to 4. The corrosion resistance to the low-k film was evaluated as follows.
A: The film thickness reduction rate is less than 0.1 nm / min and the refractive index change is less than 0.01.
X: The film thickness reduction rate is 0.1 nm / min or more and / or the refractive index change is 0.01 or more.
（４）層間絶縁膜への濡れ性評価試験
層間絶縁膜への濡れ性評価には層間絶縁膜としてＣＶＤ−ＳｉＯＣ膜チップ（膜厚５００nm、３ｃm×３ｃm、ｋ値２．５）を用いた。このチップに対する実施例１〜４の組成物の接触角を全自動接触角計（協和界面科学株式会社製ＣＡ−Ｗ）を用いて測定した。
実施例１〜４の組成物の各組成及び実験結果を表１に示す。なおｌｏｗ−ｋ膜への濡れ性は以下のように評価した。
○：ＣＶＤ−ＳｉＯＣへの接触角が水の３分の１未満。
△：ＣＶＤ−ＳｉＯＣへの接触角が水の２分の１以下３分の１以上。
×：ＣＶＤ−ＳｉＯＣへの接触角が水と同等。(4) Wetability evaluation test for interlayer insulating film For the evaluation of wettability to the interlayer insulating film, a CVD-SiOC film chip (film thickness 500 nm, 3 cm × 3 cm, k value 2.5) was used as the interlayer insulating film. The contact angles of the compositions of Examples 1 to 4 with respect to this chip were measured using a fully automatic contact angle meter (CA-W manufactured by Kyowa Interface Science Co., Ltd.).
Table 1 shows the compositions and experimental results of the compositions of Examples 1 to 4. The wettability to the low-k film was evaluated as follows.
○: The contact angle to CVD-SiOC is less than one third of water.
(Triangle | delta): The contact angle to CVD-SiOC is 1/2 or less of water and 1/3 or more of water.
X: The contact angle to CVD-SiOC is equivalent to water.
なお表１において、ＨＦはフッ化水素酸、ＮＨ４Ｆはフッ化アンモニウム、ＮＨ４Ｆ／ＨＦは酸性フッ化アンモニウム、ＤＭＡＣはＮ，Ｎ−ジメチルアセトアミド、ＢＣはジエチレングリコールモノブチルエーテル（ブチルカルビトール）、ＮＨ３はアンモニア、ＣＥＥＤＡはシアノエチルエチレンジアミンを意味する。
上記表１の結果から、実施例１〜４の組成物は、銅酸化物除去性、銅配線及びＣＶＤ−ＳｉＯＣ膜への耐腐食性が良好であり、ＣＶＤ−ＳｉＯＣ膜への濡れ性も水と比較して向上したものであることが分かった。 From the results of Table 1 above, the compositions of Examples 1 to 4 have good copper oxide removability, corrosion resistance to copper wiring and CVD-SiOC film, and wettability to CVD-SiOC film is also water. It was found that this was an improvement over that.
本発明は、特定の好ましい実施態様に関して記述されているものの、本発明の真の精神および範囲から逸脱することなく、種々の変更及び改良をこれに行い得ることは、当業者によって理解される。従って、本発明の請求の範囲は、このような全ての変更及び改良を含み、本発明の真の精神及び範囲を包含することを意図している。 Although the invention has been described with reference to certain preferred embodiments, it will be understood by those skilled in the art that various changes and modifications can be made thereto without departing from the true spirit and scope of the invention. Accordingly, the claims of the present invention are intended to embrace all such changes and modifications as to cover the true spirit and scope of the present invention.
Claims (16)
（ａ）フッ化水素酸、酸性フッ化アンモニウム及びフッ化アンモニウムからなる群から選択される少なくとも１種のフッ素化合物、
（ｂ）少なくとも１種の有機溶媒、
（ｃ）ホスホン酸、
（ｄ）アスコルビン酸、
（ｅ）少なくとも１種の塩基性化合物、及び
（ｆ）水
を含む半導体ウェハ洗浄用組成物。Used in the semiconductor wafer processing process,
(A) at least one fluorine compound selected from the group consisting of hydrofluoric acid, acidic ammonium fluoride and ammonium fluoride,
(B) at least one organic solvent,
(C) phosphonic acid,
(D) ascorbic acid,
(E) A composition for cleaning a semiconductor wafer, comprising at least one basic compound, and (f) water.
（ａ）フッ化水素酸、酸性フッ化アンモニウム及びフッ化アンモニウムからなる群から選択される少なくとも１種のフッ素化合物、
（ｂ）少なくとも１種の有機溶媒、
（ｃ）ホスホン酸、
（ｄ）アスコルビン酸、
（ｅ）少なくとも１種の塩基性化合物、及び
（ｆ）水
を含む半導体ウェハ洗浄用組成物を使用することによる半導体ウェハの洗浄方法。In the semiconductor wafer processing process,
(A) at least one fluorine compound selected from the group consisting of hydrofluoric acid, acidic ammonium fluoride and ammonium fluoride,
(B) at least one organic solvent,
(C) phosphonic acid,
(D) ascorbic acid,
(E) A method for cleaning a semiconductor wafer by using a composition for cleaning a semiconductor wafer comprising at least one basic compound and (f) water.
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| PCT/JP2006/310464 WO2006129549A1 (en) | 2005-06-01 | 2006-05-25 | Semiconductor cleaning liquid composition containing phosphonic acid and ascorbic acid, and method of cleaning |
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| JP (1) | JPWO2006129549A1 (en) |
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| US9058975B2 (en) | 2006-06-09 | 2015-06-16 | Lam Research Corporation | Cleaning solution formulations for substrates |
| JP5871562B2 (en) | 2011-11-01 | 2016-03-01 | 東京応化工業株式会社 | Stripping solution for photolithography and pattern forming method |
| JP6157081B2 (en) * | 2012-09-24 | 2017-07-05 | 東京応化工業株式会社 | Stripping solution for photolithography and pattern forming method |
| US9536730B2 (en) * | 2012-10-23 | 2017-01-03 | Air Products And Chemicals, Inc. | Cleaning formulations |
| KR101973974B1 (en) * | 2015-02-12 | 2019-04-30 | 후지필름 가부시키가이샤 | Method and apparatus for removing oxides of III-V elements, process liquids of compounds of group III-V elements, antioxidants of group III-V elements, process liquid of semiconductor substrates, and method of manufacturing semiconductor substrate products |
| KR101764577B1 (en) | 2015-08-13 | 2017-08-23 | 엘티씨 (주) | Composition of stripping solution for liquid crystal display process photoresist |
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| JP4159944B2 (en) * | 2003-07-31 | 2008-10-01 | 花王株式会社 | Resist stripping composition |
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