WO2021131452A1 - 洗浄液、洗浄方法 - Google Patents
洗浄液、洗浄方法 Download PDFInfo
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- WO2021131452A1 WO2021131452A1 PCT/JP2020/043458 JP2020043458W WO2021131452A1 WO 2021131452 A1 WO2021131452 A1 WO 2021131452A1 JP 2020043458 W JP2020043458 W JP 2020043458W WO 2021131452 A1 WO2021131452 A1 WO 2021131452A1
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- FYAQQULBLMNGAH-UHFFFAOYSA-N hexane-1-sulfonic acid Chemical compound CCCCCCS(O)(=O)=O FYAQQULBLMNGAH-UHFFFAOYSA-N 0.000 description 1
- 238000011086 high cleaning Methods 0.000 description 1
- 229960001340 histamine Drugs 0.000 description 1
- 150000003840 hydrochlorides Chemical group 0.000 description 1
- RNYJXPUAFDFIQJ-UHFFFAOYSA-N hydron;octadecan-1-amine;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[NH3+] RNYJXPUAFDFIQJ-UHFFFAOYSA-N 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910001026 inconel Inorganic materials 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- AGPKZVBTJJNPAG-UHFFFAOYSA-N isoleucine Natural products CCC(C)C(N)C(O)=O AGPKZVBTJJNPAG-UHFFFAOYSA-N 0.000 description 1
- 229960000310 isoleucine Drugs 0.000 description 1
- 150000002527 isonitriles Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 230000015654 memory Effects 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- LFETXMWECUPHJA-UHFFFAOYSA-N methanamine;hydrate Chemical compound O.NC LFETXMWECUPHJA-UHFFFAOYSA-N 0.000 description 1
- IBKQQKPQRYUGBJ-UHFFFAOYSA-N methyl gallate Natural products CC(=O)C1=CC(O)=C(O)C(O)=C1 IBKQQKPQRYUGBJ-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- VMESOKCXSYNAKD-UHFFFAOYSA-N n,n-dimethylhydroxylamine Chemical compound CN(C)O VMESOKCXSYNAKD-UHFFFAOYSA-N 0.000 description 1
- KRKPYFLIYNGWTE-UHFFFAOYSA-N n,o-dimethylhydroxylamine Chemical compound CNOC KRKPYFLIYNGWTE-UHFFFAOYSA-N 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- DYUSVPKMWAMYDH-UHFFFAOYSA-N n-ethoxyethanamine Chemical compound CCNOCC DYUSVPKMWAMYDH-UHFFFAOYSA-N 0.000 description 1
- CPQCSJYYDADLCZ-UHFFFAOYSA-N n-methylhydroxylamine Chemical compound CNO CPQCSJYYDADLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000006199 nebulizer Substances 0.000 description 1
- 229910000623 nickel–chromium alloy Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical group 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 125000000018 nitroso group Chemical group N(=O)* 0.000 description 1
- KPADFPAILITQBG-UHFFFAOYSA-N non-4-ene Chemical compound CCCCC=CCCC KPADFPAILITQBG-UHFFFAOYSA-N 0.000 description 1
- AQFWNELGMODZGC-UHFFFAOYSA-N o-ethylhydroxylamine Chemical compound CCON AQFWNELGMODZGC-UHFFFAOYSA-N 0.000 description 1
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- UHGIMQLJWRAPLT-UHFFFAOYSA-N octadecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCCCCCCCOP(O)(O)=O UHGIMQLJWRAPLT-UHFFFAOYSA-N 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- WLGDAKIJYPIYLR-UHFFFAOYSA-N octane-1-sulfonic acid Chemical compound CCCCCCCCS(O)(=O)=O WLGDAKIJYPIYLR-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- NPKKRSHVJIQBKU-UHFFFAOYSA-N ornogenin Natural products CC(OC(=O)C=Cc1ccccc1)C2(O)CCC3(O)C4(O)CC=C5CC(O)CCC5(C)C4CC(OC(=O)C=Cc6ccccc6)C23C NPKKRSHVJIQBKU-UHFFFAOYSA-N 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229960005152 pentetrazol Drugs 0.000 description 1
- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Natural products OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 0.000 description 1
- YZTJYBJCZXZGCT-UHFFFAOYSA-N phenylpiperazine Chemical compound C1CNCCN1C1=CC=CC=C1 YZTJYBJCZXZGCT-UHFFFAOYSA-N 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- UCZIPIUJGGENPL-UHFFFAOYSA-N piperazin-2-ol Chemical compound OC1CNCCN1 UCZIPIUJGGENPL-UHFFFAOYSA-N 0.000 description 1
- SIRSTRHGFGFVME-UHFFFAOYSA-N piperazin-2-ylmethanol Chemical compound OCC1CNCCN1 SIRSTRHGFGFVME-UHFFFAOYSA-N 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001444 polymaleic acid Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 150000003212 purines Chemical class 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 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 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 239000012487 rinsing solution Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229950005425 sodium myristyl sulfate Drugs 0.000 description 1
- ICQIPNSTIFKYFS-UHFFFAOYSA-M sodium;3-(2,3-dihydroxypropylsulfanyl)-2-methylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(C)CSCC(O)CO ICQIPNSTIFKYFS-UHFFFAOYSA-M 0.000 description 1
- ODBPOHVSVJZQRX-UHFFFAOYSA-M sodium;[2-[2-[bis(phosphonomethyl)amino]ethyl-(phosphonomethyl)amino]ethyl-(phosphonomethyl)amino]methyl-hydroxyphosphinate Chemical compound [Na+].OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)([O-])=O ODBPOHVSVJZQRX-UHFFFAOYSA-M 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- PWEBUXCTKOWPCW-UHFFFAOYSA-N squaric acid Chemical compound OC1=C(O)C(=O)C1=O PWEBUXCTKOWPCW-UHFFFAOYSA-N 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 229910001256 stainless steel alloy Inorganic materials 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 1
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 1
- 229940117986 sulfobetaine Drugs 0.000 description 1
- 125000002130 sulfonic acid ester group Chemical group 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical group 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- KRIXEEBVZRZHOS-UHFFFAOYSA-N tetradecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCCCOP(O)(O)=O KRIXEEBVZRZHOS-UHFFFAOYSA-N 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- VHLDQAOFSQCOFS-UHFFFAOYSA-M tetrakis(2-hydroxyethyl)azanium;hydroxide Chemical compound [OH-].OCC[N+](CCO)(CCO)CCO VHLDQAOFSQCOFS-UHFFFAOYSA-M 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- NJRXVEJTAYWCQJ-UHFFFAOYSA-N thiomalic acid Chemical compound OC(=O)CC(S)C(O)=O NJRXVEJTAYWCQJ-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- MAKDTFFYCIMFQP-UHFFFAOYSA-N titanium tungsten Chemical compound [Ti].[W] MAKDTFFYCIMFQP-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- WYXIGTJNYDDFFH-UHFFFAOYSA-Q triazanium;borate Chemical compound [NH4+].[NH4+].[NH4+].[O-]B([O-])[O-] WYXIGTJNYDDFFH-UHFFFAOYSA-Q 0.000 description 1
- GAJQCIFYLSXSEZ-UHFFFAOYSA-L tridecyl phosphate Chemical compound CCCCCCCCCCCCCOP([O-])([O-])=O GAJQCIFYLSXSEZ-UHFFFAOYSA-L 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 1
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 239000004474 valine Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- 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
- C11D3/33—Amino carboxylic acids
-
- 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
- H01L21/02074—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers the processing being a planarization 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/28—Heterocyclic compounds containing nitrogen in the ring
-
- 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
- C11D3/30—Amines; Substituted amines ; Quaternized amines
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/36—Organic compounds containing phosphorus
- C11D3/361—Phosphonates, phosphinates or phosphonites
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
- C11D7/3209—Amines or imines with one to four nitrogen atoms; Quaternized amines
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
- C11D7/3218—Alkanolamines or alkanolimines
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
- C11D7/3245—Aminoacids
-
- 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
- C11D7/3281—Heterocyclic 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
- C11D7/34—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
- C11D7/22—Organic compounds
- C11D7/36—Organic compounds containing phosphorus
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/304—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
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/14—Hard surfaces
- C11D2111/22—Electronic devices, e.g. PCBs or semiconductors
Definitions
- the present invention relates to a cleaning liquid for a semiconductor substrate and a method for cleaning a semiconductor substrate.
- Semiconductor elements such as CCDs (Charge-Coupled Devices) and memories are manufactured by forming fine electronic circuit patterns on a substrate using photolithography technology. Specifically, a resist film is formed on a laminate having a metal film as a wiring material, an etching stop layer, and an interlayer insulating layer on a substrate, and a photolithography step and a dry etching step (for example, plasma etching treatment). By carrying out the above, a semiconductor element is manufactured.
- a dry etching residue for example, a metal component such as a titanium-based metal derived from a metal hard mask or an organic component derived from a photoresist film
- CMP chemical mechanical polishing
- a polishing slurry containing polishing fine particles for example, silica, alumina, etc.
- Mechanical Polishing processing may be performed.
- the polished fine particles used in the CMP treatment, the polished wiring metal film, and / or the metal component derived from the barrier metal and the like tend to remain on the surface of the semiconductor substrate after polishing. Since these residues can short-circuit the wiring and affect the electrical characteristics of the semiconductor, a cleaning step of removing these residues from the surface of the semiconductor substrate is often performed.
- Patent Document 1 describes an aqueous cleaning composition for after chemical and mechanical flattening of copper, which comprises an organic base, a copper etching agent, an organic ligand, a corrosion inhibitor which is a hydrazide compound, and water.
- a composition containing a specific concentration of an organic base, a copper etching agent, an organic ligand, and a corrosion inhibitor is described.
- the present inventor has examined a cleaning liquid for a semiconductor substrate to which CMP has been applied with reference to Patent Document 1 and the like.
- a residue containing copper and a residue containing cobalt remain on the surface of the semiconductor substrate, the cleaning liquid It was found that the reaction rates of the components contained in the above with respect to these residues were significantly different, and it was found that there is room for further improvement in the cleaning performance and corrosion prevention performance of the cleaning liquid for the semiconductor substrate subjected to CMP.
- a cleaning solution for a semiconductor substrate subjected to a chemical mechanical polishing treatment which is at least one component selected from the group consisting of a component A, which is an amino acid having one carboxyl group, and an aminopolycarboxylic acid and a polyphosphonic acid.
- B and a component C which is an aliphatic amine (however, the above component A, the above amino polycarboxylic acid, and the quaternary ammonium compound are excluded), and the content of the above component B relative to the content of the above component A
- the cleaning liquid has a mass ratio of 0.2 to 10, and a mass ratio of the content of the component C to the sum of the content of the component A and the content of the component B is 5 to 100.
- the component B is at least one selected from the group consisting of diethylenetriamine pentaacetic acid, ethylenediaminetetraacetic acid, trans-1,2-diaminocyclohexanetetraacetic acid, nitrilotris (methylenephosphonic acid) and ethylenediaminetetra (methylenephosphonic acid).
- a method for cleaning a semiconductor substrate which comprises a step of applying the cleaning liquid according to any one of [1] to [13] to a semiconductor substrate subjected to a chemical mechanical polishing treatment for cleaning.
- a cleaning liquid for a semiconductor substrate to which CMP has been applied which is excellent in cleaning performance and corrosion prevention performance for a metal film containing copper and a metal film containing cobalt. Further, according to the present invention, it is possible to provide a method for cleaning a semiconductor substrate to which CMP has been applied.
- the numerical range represented by using "-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
- the “content” of the component means the total content of the two or more kinds of components.
- “ppm” means “parts-per-million ( 10-6 )”
- ppb means “parts-per-billion ( 10-9 )”.
- the compounds described in the present specification may contain isomers (compounds having the same number of atoms but different structures), optical isomers, and isotopes. Further, only one kind of isomer and isotope may be contained, or a plurality of kinds may be contained.
- the cleaning liquid of the present invention is a cleaning liquid for a semiconductor substrate subjected to a chemical mechanical polishing treatment (CMP), and contains a component A which is an amino acid having one carboxyl group.
- CMP chemical mechanical polishing treatment
- the mass ratio of the content of the component B to the content of the component A is 0.05 to 20.
- the mass ratio of the content of the component C to the sum of the content of the component A and the content of the component B is 5 to 100.
- the cleaning liquid contains component A, component B and component C, and the ratio of the contents of component A, component B and component C is specified, so that the semiconductor substrate to which CMP is applied is subjected to CMP.
- the cleaning performance and corrosion prevention performance for a metal film containing copper and a metal film containing cobalt in a cleaning step are improved.
- the description that "the semiconductor substrate has a metal film containing copper and a metal film containing cobalt” means that the metal film containing copper and the metal film containing cobalt are the same. It means both the case where it is a metal film (that is, the case where a single metal film contains both copper and cobalt) and the case where both are different metal films.
- the reaction rate to cobalt is found that 10 2 to 10 8 degrees slower than the reaction rate of the copper. Therefore, when a residue containing copper (hereinafter, also referred to as “Cu residue”) and a residue containing cobalt (hereinafter, also referred to as “Co residue”) remain on the surface of the semiconductor substrate, the cleaning component Co contained in the cleaning liquid is contained. It was found that the reactivity to the residue is low and it may be difficult to obtain high cleaning performance.
- the cleaning liquid of the present invention uses a specific content of component A, which has a relatively close reaction rate to cobalt and a reaction rate to copper, to form a semiconductor substrate for a metal film containing copper and a metal film containing cobalt.
- component A which has a relatively close reaction rate to cobalt and a reaction rate to copper
- the present inventor presumes that the corrosion prevention performance and the cleaning performance of the Cu residue were excellent, and the cleaning performance of the Co residue could be improved.
- the cleaning solution contains a component A, which is an amino acid having one carboxyl group.
- the component A is not particularly limited as long as it is a compound having one carboxyl group and one or more amino groups in the molecule.
- Examples of component A include glycine, serine, ⁇ -alanine (2-aminopropionic acid), ⁇ -alanine (3-aminopropionic acid), lysine, leucine, isoleucine, cysteine, methionine, ethionine, threonine, tryptophan, and tyrosine.
- JP-A-2016-086094 Valine, histidine, histidine derivatives, asparagine, glutamine, arginine, proline, phenylalanine, the compounds described in paragraphs [0021] to [0023] of JP-A-2016-086094, and salts thereof.
- the histidine derivative the compounds described in JP-A-2015-165651 and JP-A-2015-165562 can be incorporated, and the contents thereof are incorporated in the present specification.
- the salt include alkali metal salts such as sodium salt and potassium salt, ammonium salt, carbonate, and acetate.
- the number of amino groups contained in the component A is preferably 1 to 4, more preferably 1 or 2, and even more preferably 1.
- the component A preferably has a low molecular weight. Specifically, the molecular weight of the component A is preferably 600 or less, more preferably 450 or less, and even more preferably 300 or less.
- the lower limit is not particularly limited, and is preferably 70 or more.
- the carbon number of the component A is preferably 15 or less, more preferably 12 or less, and even more preferably 8 or less.
- the lower limit is not particularly limited, and is preferably 1 or more.
- glycine, histidine, cysteine, arginine, methionine, sarcosine or alanine are preferable in that the cleaning performance (particularly the cleaning performance for a metal film containing Co) is more excellent, and glycine is further excellent in cleaning performance. Histidine, cysteine or alanine is more preferred, and glycine, histidine, or alanine is even more preferred.
- the reaction rate for the Co 2+ is preferably from 10 4 to 10 9, 10 6 to 10 9 Is more preferable.
- the reaction rate as the compound is 10 4 to 10 9, glycine, histidine, cysteine, methionine or alanine.
- the reaction rate (solvent exchange rate) of the compound to Co 2+ can be carried out by cooling with a cryostud and tracking the increase or decrease in peak absorption by continuous measurement with a spectrophotometer. For example, it can be measured by tracking spectral peaks appearing at wavelengths of 400-700 nm under liquid nitrogen temperature (77K). Since the reaction rate here is the reaction rate at 23 ° C., the measurement temperature is converted to the room temperature temperature.
- the content of component A in the cleaning liquid is preferably 0.003% by mass or more, preferably 0.005% by mass, based on the total mass of the cleaning liquid, in that the cleaning performance (particularly the cleaning performance for a metal film containing Co) is more excellent.
- the above is more preferable, and 0.01% by mass or more is further preferable.
- the upper limit is not particularly limited, but is preferably 2.0% by mass or less, preferably 1.0% by mass or less, based on the total mass of the cleaning liquid, in that it is excellent in corrosion prevention performance (particularly, cleaning performance for a metal film containing Cu or Co).
- the content of component A is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, and more preferably 0.05% by mass or more, based on the total mass of the components in the cleaning liquid excluding the solvent. More preferred.
- the upper limit is not particularly limited, but is preferably 15.0% by mass or less, more preferably 10.0% by mass or less, and further preferably 8.0% by mass or less, based on the total mass of the components excluding the solvent in the cleaning liquid. ..
- the "total mass of the components excluding the solvent in the cleaning solution” means the total content of all the components contained in the cleaning solution other than the solvent.
- solvent simply includes both water and organic solvents.
- the cleaning solution contains component B, which is at least one selected from the group consisting of aminopolycarboxylic acid and polyphosphonic acid.
- Aminopolycarboxylic acid is a compound having one or more amino groups and two or more carboxyl groups in the molecule.
- Polyphosphonic acid is a compound having two or more phosphonic acid groups in the molecule.
- Aminopolycarboxylic acid is a compound having one or more amino groups and two or more carboxy groups as coordinating groups in the molecule.
- Examples of aminopolycarboxylic acids include asparaginic acid, glutamate, butylenediaminetetraacetic acid, diethylenetriaminetetraacetic acid (DTPA), ethylenediaminetetrapropionic acid, triethylenediaminetetraminehexacetic acid, 1,3-diamino-2-hydroxypropane-N, N, N', N'-tetraacetic acid, propylenediaminetetraacetic acid, ethylenediaminetetraacetic acid (EDTA), trans-1,2-diaminocyclohexanetetraacetic acid (CyDTA), ethylenediaminediaminediamine, ethylenediaminediaminedipropionic acid, 1,6- Hexamethylene-diamine-N, N, N
- the number of amino groups contained in the aminopolycarboxylic acid is preferably 1 to 5, more preferably 2 to 4, and even more preferably 3 or 4.
- the number of carboxyl groups contained in the aminopolycarboxylic acid is preferably 2 to 5, more preferably 3 to 5, and even more preferably 4 or 5.
- the carbon number of the aminopolycarboxylic acid is preferably 15 or less, more preferably 12 or less.
- the lower limit is not particularly limited, and is preferably 4 or more, and more preferably 6 or more.
- As the aminopolycarboxylic acid, DTPA, EDTA or CyDTA is preferable, and DTPA or EDTA is more preferable, in that the cleaning performance (particularly the cleaning performance for a metal film containing Cu) is more excellent.
- Polyphosphonic acid is a compound having two or more phosphonic acid groups in the molecule.
- Examples of the polyphosphonic acid include compounds represented by the following formulas (P1), (P2) and (P3).
- X represents a hydrogen atom or a hydroxy group
- R 1 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
- Alkyl group having 1 to 10 carbon atoms represented by R 1 in formula (P1) may be any of linear, branched and cyclic.
- the R 1 in the formula (P1) preferably an alkyl group having 1 to 6 carbon atoms, a methyl group, an ethyl group, n- propyl group, or isopropyl group is more preferable.
- n- represents a normal- form.
- a hydroxy group is preferable as X in the formula (P1).
- Examples of the polyphosphonic acid represented by the formula (P1) include ethylidene diphosphonic acid, 1-hydroxyethylidene-1,1'-diphosphonic acid (HEDPO), 1-hydroxypropyridene-1,1'-diphosphonic acid, or 1 -Hydroxybutylidene-1,1'-diphosphonic acid is preferred.
- HEDPO 1-hydroxyethylidene-1,1'-diphosphonic acid
- 1 -Hydroxybutylidene-1,1'-diphosphonic acid is preferred.
- Q represents a hydrogen atom or R 3- PO 3 H 2
- R 2 and R 3 each independently represent an alkylene group
- Y represents a hydrogen atom, -R 3- PO 3 H 2.
- P4 a group represented by the following formula (P4).
- Q and R 3 are the same as Q and R 3 in the formula (P2).
- the alkylene group represented by R 2 in formula (P2) for example, straight-chain or branched alkylene group having 1 to 12 carbon atoms.
- the alkylene group represented by R 2 preferably a linear or branched alkylene group having 1 to 6 carbon atoms, more preferably a linear or branched alkylene group having 1 to 4 carbon atoms, Ethylene groups are more preferred.
- the alkylene group represented by R 3 in formula (P2) and (P4) for example, linear or branched alkylene group having 1 to 10 carbon atoms, having 1 to 4 linear or carbon
- a branched alkylene group is preferable, a methylene group or an ethylene group is more preferable, and a methylene group is further preferable.
- -R 3- PO 3 H 2 is preferable.
- Y in the formula (P2) a group represented by -R 3- PO 3 H 2 or the formula (P4) is preferable, and a group represented by the formula (P4) is more preferable.
- Examples of the polyphosphonic acid represented by the formula (P2) include ethylaminobis (methylenephosphonic acid), dodecylaminobis (methylenephosphonic acid), nitrilotris (methylenephosphonic acid) (NTPO), and ethylenediaminebis (methylenephosphonic acid) (methylenephosphonic acid).
- EDDPO 1,3-propylene diaminebis (methylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid) (EDTPO), ethylenediaminetetra (ethylenephosphonic acid), 1,3-propylenediaminetetra (methylenephosphonic acid) (PDTMP) , 1,2-Diaminopropanetetra (methylenephosphonic acid), or 1,6-hexamethylenediaminetetra (methylenephosphonic acid) is preferable.
- R 4 and R 5 each independently represents an alkylene group having 1 to 4 carbon atoms
- n represents an integer of 1-4
- One represents an alkyl group having a phosphonic acid group
- the rest represents an alkyl group.
- the alkylene group having 1 to 4 carbon atoms represented by R 4 and R 5 in the formula (P3) may be either linear or branched.
- Examples of the alkylene group having 1 to 4 carbon atoms represented by R 4 and R 5 include a methylene group, an ethylene group, a propylene group, a trimethylene group, an ethylmethylene group, a tetramethylene group, a 2-methylpropylene group, and 2-. Examples thereof include a methyltrimethylene group and an ethylethylene group, and an ethylene group is preferable.
- n in the formula (P3) 1 or 2 is preferable.
- Examples of the alkyl group in the alkyl group represented by Z 1 to Z 5 in the formula (P3) and the alkyl group having a phosphonic acid group include a linear or branched alkyl group having 1 to 4 carbon atoms.
- the methyl group is preferred.
- the number of phosphonic acid groups in the alkyl group having a phosphonic acid group represented by Z 1 to Z 5 is preferably one or two, and more preferably one.
- Examples of the alkyl group having a phosphonic acid group represented by Z 1 to Z 5 include a linear or branched alkyl group having 1 to 4 carbon atoms and having one or two phosphonic acid groups.
- (Mono) phosphonomethyl group or (mono) phosphonoethyl group is preferable, and (mono) phosphonomethyl group is more preferable.
- Z 1 to Z 5 in the formula (P3) it is preferable that all of Z 1 to Z 4 and n Z 5 are alkyl groups having the above phosphonic acid groups.
- Examples of the polyphosphonic acid represented by the formula (P3) include diethylenetriaminepenta (methylenephosphonic acid) (DEPPO), diethylenetriaminepenta (ethylenephosphonic acid), triethylenetetraminehexa (methylenephosphonic acid), or triethylenetetraminehexa (ethylenephosphon). Acid) is preferred.
- the polyphosphonic acid used in the washing liquid includes not only the polyphosphonic acid represented by the above formulas (P1), (P2) and (P3), but also paragraphs [0026] to [0036] to [0036] of International Publication No. 2018/020878. ], And the compounds ((co) polymers) described in paragraphs [0031] to [0046] of International Publication No. 2018/030006 can be incorporated, and the contents thereof are incorporated in the present specification. Is done.
- the number of phosphonic acid groups contained in the polyphosphonic acid is preferably 2 to 5, more preferably 2 to 4, and even more preferably 3 or 4.
- the carbon number of the polyphosphonic acid is preferably 15 or less, more preferably 12 or less, and even more preferably 8 or less.
- the lower limit is not particularly limited, and is preferably 3 or more.
- the polyphosphonic acid the compounds listed as suitable specific examples in each of the polyphosphonic acids represented by the above formulas (P1), (P2) and (P3) are preferable, and cleaning performance (particularly cleaning of a metal film containing Cu) is preferable.
- NTPO or EDTPO is more preferable, and EDTPO is further preferable in that the performance) is more excellent.
- Component B preferably has a low molecular weight. Specifically, the molecular weight of the component B is preferably 600 or less, more preferably 450 or less. The lower limit is not particularly limited, and is preferably 100 or more.
- component B diethylenetriaminetetraacetic acid (DTPA), ethylenediaminetetraacetic acid (EDTA), and trans-1,2-diaminocyclohexanetetraacetic acid (CyDTA) are more excellent in cleaning performance (particularly cleaning performance for metal films containing Cu).
- DTPA diethylenetriaminetetraacetic acid
- EDTA ethylenediaminetetraacetic acid
- CyDTA trans-1,2-diaminocyclohexanetetraacetic acid
- NTPO Nitrilotris (methylenephosphonic acid)
- EDTPO ethylenediaminetetra (methylenephosphonic acid)
- DTPA ethylenediaminetetra
- CyDTA ethylenediaminetetra
- EDTPO ethylenediaminetetra
- the first complex generation constant K m1 with respect to Co 2+ is preferably 10 to 30, more preferably 15 to 30, in that the cleaning performance for the metal film containing Co is more excellent.
- examples of the compound having the first complex generation constant K m1 of 10 to 30 include DTPA, EDTA, CyDTA and TTHA.
- the first complex formation constant K m1 of the compound is obtained by the following known method. That is, the binding constant (complexation constant) in the chelate formation reaction between the metal and the ligand is obtained by the following formula (1).
- M is a metal
- L is a ligand
- KML is a binding constant.
- the variables related to the concentration of each component required for this calculation are not particularly limited as long as they have a primary correspondence with each concentration, and for example, known methods such as ultraviolet-visible spectroscopic measurement, fluorescence intensity measurement, and NMR measurement can be used. Variables such as measured concentration and absorbance can be applied.
- component B one type may be used alone, or two or more types may be used in combination.
- the content of component B in the cleaning liquid is not particularly limited, but is preferably 0.005% by mass or more, preferably 0.008% by mass or more, based on the total mass of the cleaning liquid, in that it is superior in cleaning performance to a metal film containing Cu. Is more preferable, and 0.01% by mass or more is further preferable.
- the upper limit is not particularly limited, but 2.0% by mass or less is preferable, and 1.5% by mass or less is preferable with respect to the total mass of the cleaning liquid in that it is excellent in corrosion prevention performance (particularly corrosion prevention performance for metal films containing Cu). More preferably, 1.2% by mass or less is further preferable.
- the content of component B is preferably 0.02% by mass or more, more preferably 0.05% by mass or more, and 0.1% by mass or more, based on the total mass of the components in the cleaning liquid excluding the solvent. More preferred.
- the upper limit is not particularly limited, but is preferably 20.0% by mass or less, more preferably 15.0% by mass or less, still more preferably 10.0% by mass or less, based on the total mass of the components excluding the solvent in the cleaning liquid. ..
- the mass ratio of the content of component B (content of component B / content of component A) to the content of component A is 0.2 to 10.
- the mass ratio of the content of the component B to the content of the component A is preferably 0.2 to 5, more preferably 0.5 to 3.
- the cleaning solution contains an aliphatic amine as component C.
- the aliphatic amine as the component C does not include the component A, the aminopolycarboxylic acid as the component B, and the quaternary ammonium compound.
- the aliphatic amine examples include a primary amine having a primary amino group (-NH 2 ) in the molecule, a secondary amine having a secondary amino group (> NH) in the molecule, and an aliphatic amine in the molecule. At least one selected from the group consisting of tertiary amines having a tertiary amino group (> N-) and salts thereof, which do not have an aromatic ring, and the above-mentioned component A, aminopoly.
- the compound is not particularly limited as long as it is not contained in the carboxylic acid and the quaternary ammonium compound.
- Examples of the salt of at least one selected from the group consisting of primary amines, secondary amines and tertiary amines include Cl and S. , N, and a salt of an inorganic acid in which at least one non-metal selected from the group consisting of N and P is bonded to hydrogen, and hydrochlorides, sulfates, or nitrates are preferable.
- Examples of the component C include amino alcohols, alicyclic amines, and aliphatic monoamine compounds and aliphatic polyamine compounds other than amino alcohols and alicyclic amines.
- Amino alcohols are compounds of primary to tertiary amines that further have at least one hydroxylalkyl group in the molecule.
- the amino alcohol may have any of primary to tertiary amino groups, but preferably has a primary amino group.
- amino alcohols examples include monoethanolamine (MEA), 2-amino-2-methyl-1-propanol (AMP), diethanolamine (DEA), triethanolamine (TEA), diethylene glycolamine (DEGA), and trishydroxymethyl.
- Examples include aminomethane (Tris), 2- (methylamino) -2-methyl-1-propanol (N-MAMP) and 2- (2-aminoethylamino) ethanol.
- AMP, N-MAMP, MEA, DEA, Tris or DEGA are preferable, and AMP is more preferable.
- the alicyclic amine compound is not particularly limited as long as it is a compound having a non-aromatic heterocycle in which at least one of the atoms constituting the ring is a nitrogen atom.
- Examples of the alicyclic amine compound include a piperazine compound and a cyclic amidine compound.
- the piperazine compound is a compound having a hetero 6-membered ring (piperazine ring) in which the opposite -CH- group of the cyclohexane ring is replaced with a nitrogen atom.
- the piperazine compound may have a substituent on the piperazine ring. Examples of such a substituent include a hydroxy group, an alkyl group having 1 to 4 carbon atoms which may have a hydroxy group, and an aryl group having 6 to 10 carbon atoms.
- piperazine compound examples include piperazine, 1-methylpiperazine, 1-ethylpiperazine, 1-propylpiperazine, 1-butylpiperazine, 2-methylpiperazine, 1,4-dimethylpiperazine, 2,5-dimethylpiperazine, 2, 6-Dimethylpiperazine, 1-phenylpiperazine, 2-hydroxypiperazine, 2-hydroxymethylpiperazine, 1- (2-hydroxyethyl) piperazine (HEP), N- (2-aminoethyl) piperazine (AEP), 1,4 Examples include -bis (2-hydroxyethyl) piperazine (BHEP), 1,4-bis (2-aminoethyl) piperazine (BAEP), and 1,4-bis (3-aminopropyl) piperazine (BAPP). , 1-Methylpiperazine, 2-Methylpiperazine, HEP, AEP, BHEP, BAEP or BAPP are preferred, and piperazine is more preferred.
- the number of ring members of the above heterocycle contained in the cyclic amidine compound is not particularly limited, but is preferably 5 or 6, and more preferably 6.
- Examples of the cyclic amidine compound include diazabicycloundecene (1,8-diazabicyclo [5.4.0] undec-7-ene: DBU) and diazabicyclononene (1,5-diazabicyclo [4.3.3.
- Nona-5-en DBN
- 3,4,6,7,8,9,10,11-octahydro-2H-pyrimid [1.2-a] azocin
- 3,4,6,7,8 9-Hexahydro-2H-pyrido [1.2-a] pyrimidine
- 2,5,6,7-tetrahydro-3H-pyrrolo [1.2-a] imidazole 3-ethyl-2,3,4,6 , 7,8,9,10-octahydropyrimid [1.2-a] azepine, and creatinine.
- the alicyclic amine compound includes, for example, 1,3-dimethyl-2-imidazolidinone, a non-aromatic hetero5-membered ring compound such as imidazolidinethione, and a nitrogen atom.
- examples include compounds having a 7-membered ring.
- aliphatic monoamine compound other than the amino alcohol and the alicyclic amine examples include a compound represented by the following formula (a) (hereinafter, also referred to as “compound (a)”).
- NH x R (3-x) (a) R represents an alkyl group having 1 to 3 carbon atoms, and x represents an integer of 0 to 2.
- the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, an n-propyl group and an isopropyl group, and an ethyl group or an n-propyl group is preferable.
- Examples of the compound (a) include methylamine, ethylamine, propylamine, dimethylamine, diethylamine, trimethylamine, and triethylamine, and ethylamine, propylamine, diethylamine, and triethylamine are preferable.
- Examples of the aliphatic monoamine compound other than the compound (a) include n-butylamine, 3-methoxypropylamine, tert-butylamine, n-hexylamine, cyclohexylamine, n-octylamine, 2-ethylhexylamine, and 4-.
- (2-Aminoethyl) morpholin (AEM) can be mentioned.
- aliphatic polyamine compounds other than aminoalcohol and alicyclic amine examples include ethylenediamine (EDA), 1,3-propanediamine (PDA), 1,2-propanediamine, 1,3-butanediamine, and 1, Examples thereof include alkylene diamines such as 4-butanediamine, and polyalkyl polyamines such as diethylenetriamine (DETA), triethylenetetramine (TETA), bis (aminopropyl) ethylenediamine (BAPEDA) and tetraethylenepentamine.
- EDA ethylenediamine
- PDA 1,3-propanediamine
- TETA triethylenetetramine
- BAPEDA bis (aminopropyl) ethylenediamine
- the component C preferably further has one or more hydrophilic groups in addition to one primary to tertiary amino group.
- the hydrophilic group include primary to tertiary amino groups and hydroxy groups.
- Such amine compounds include amino alcohols having one or more primary to tertiary amino groups and one or more hydroxy groups, and aliphatics having two or more primary to tertiary amino groups. Examples thereof include polyamine compounds and alicyclic amine compounds having two or more hydrophilic groups.
- the upper limit of the total number of hydrophilic groups contained in the component C is not particularly limited, but is preferably 5 or less, and more preferably 4 or less.
- an amino alcohol or an alicyclic amine compound is preferable, and monoethanolamine (MEA), 2-amino-2-methyl-1-propanol (AMP), 2- (methylamino) -2-methyl-1 -Propanol (N-MAMP), Diethanolamine (DEA), Diethylene Glycolamine (DEGA), Trishydroxymethylaminomethane (Tris), Piperazine, N- (2-Aminoethyl) Piperazine (AEP), 1,4-Bis (2) -Hydroxyethyl) piperazine (BHEP), 1,4-bis (2-aminoethyl) piperazine (BAEP), or 1,4-bis (3-aminopropyl) piperazine (BAPP) is more preferred, AMP, MEA or Tris is more preferred.
- MEA monoethanolamine
- AMP 2-amino-2-methyl-1-propanol
- DEA 2- (methylamino) -2-methyl-1 -Propanol
- DEGA Diethylene Glycol
- the component C may be used alone or in combination of two or more.
- the content of component C in the cleaning liquid is not particularly limited, but is preferably 0.03 to 30% by mass, more preferably 0.05 to 15% by mass, and 0.5 to 12% by mass with respect to the total mass of the cleaning liquid. Is more preferable.
- the content of component C is preferably 3.0 to 99.0% by mass, more preferably 5.0 to 98.0% by mass, more preferably 20% by mass, based on the total mass of the components in the cleaning liquid excluding the solvent. .0 to 95.0% by mass is more preferable.
- the mass of the content of the component C with respect to the sum of the content of the component A and the content of the component B (content of the component C / (content of the component A + content of the component B)).
- the ratio is 5 to 100.
- the corrosion prevention performance (particularly the corrosion prevention performance for the metal film containing Cu and / or Co) is excellent, and when the mass ratio is 100 or less, the cleaning performance (particularly the metal film containing Cu) is excellent. Excellent cleaning performance).
- the mass ratio of the content of the component C to the sum of the content of the component A and the content of the component B is preferably 5 to 80, more preferably 10 to 70.
- the cleaning liquid preferably contains water as a solvent.
- the type of water used for the cleaning liquid is not particularly limited as long as it does not adversely affect the semiconductor substrate, and distilled water, deionized water, and pure water (ultrapure water) can be used. Pure water is preferable because it contains almost no impurities and has less influence on the semiconductor substrate in the manufacturing process of the semiconductor substrate.
- the water content in the cleaning liquid may be the balance of component A, component B, component C, and any component described later.
- the water content is, for example, preferably 1% by mass or more, more preferably 30% by mass or more, further preferably 60% by mass or more, and particularly preferably 85% by mass or more, based on the total mass of the cleaning liquid.
- the upper limit is not particularly limited, but is preferably 99% by mass or less, more preferably 95% by mass or less, based on the total mass of the cleaning liquid.
- the cleaning liquid may contain other optional components in addition to the above-mentioned components.
- the optional components will be described.
- the cleaning liquid is at least one selected from the group consisting of nitrogen-containing heteroaromatic compounds, reducing agents, anionic surfactants, and chelating agents (excluding compounds contained in component A, component B, and component C). It may contain the component D which is.
- the nitrogen-containing heteroaromatic compound is not particularly limited as long as it is a compound having a heteroaromatic ring (nitrogen-containing heteroaromatic ring) in which at least one of the atoms constituting the ring is a nitrogen atom.
- the nitrogen-containing heteroaromatic compound functions as an anticorrosive agent for improving the corrosion prevention performance of the cleaning liquid. Therefore, the cleaning liquid preferably contains a nitrogen-containing heteroaromatic compound.
- the nitrogen-containing heteroaromatic compound is not particularly limited, and examples thereof include an azole compound, a pyridine compound, a pyrazine compound, and a pyrimidine compound.
- the azole compound is a compound having at least one nitrogen atom and having an aromatic hetero5-membered ring.
- the number of nitrogen atoms contained in the hetero 5-membered ring of the azole compound is not particularly limited, and is preferably 2 to 4, more preferably 3 or 4.
- the azole compound may have a substituent on the hetero 5-membered ring. Examples of such a substituent include a hydroxy group, a carboxy group, a mercapto group, an amino group, an alkyl group having 1 to 4 carbon atoms which may have an amino group, and a 2-imidazolyl group.
- the azole compound include an imidazole compound, a pyrazole compound, a thiazole compound, a triazole compound, and a tetrazole compound.
- imidazole compound examples include imidazole, 1-methylimidazole, 2-methylimidazole, 5-methylimidazole, 1,2-dimethylimidazole, 2-mercaptoimidazole, 4,5-dimethyl-2-mercaptoimidazole, 4-hydroxy.
- Examples include imidazole, 2,2'-biimidazole, 4-imidazole carboxylic acid, histamine, benzoimidazole, 2-aminobenzoimidazole, and adenine.
- pyrazole compound examples include pyrazole, 4-pyrazolecarboxylic acid, 1-methylpyrazole, 3-methylpyrazole, 3-amino-5-hydroxypyrazole, 3-amino-5-methylpyrazole, 3-aminopyrazole, and 4 -Aminopyrazole can be mentioned.
- thiazole compound examples include 2,4-dimethylthiazole, benzothiazole, and 2-mercaptobenzothiazole.
- triazole compound examples include 1,2,4-triazol, 3-methyl-1,2,4-triazole, 3-amino-1,2,4-triazole, 1,2,3-triazol. -L, 1-methyl-1,2,3-triazole, benzotriazole, 1-hydroxybenzotriazole, 1-dihydroxypropylbenzotriazole, 2,3-dicarboxypropylbenzotriazole, 4-hydroxybenzotriazole, 4 -Carboxybenzotriazole and 5-methylbenzotriazole can be mentioned.
- tetrazole compound examples include 1H-tetrazole (1,2,3,4-tetrazole), 5-methyl-1,2,3,4-tetrazole and 5-amino-1,2,3.
- examples thereof include 4-tetrazole, 1,5-pentamethylenetetrazole, 1-phenyl-5-mercaptotetrazole, and 1- (2-dimethylaminoethyl) -5-mercaptotetrazole.
- an imidazole compound or a pyrazole compound is preferable, and 2-aminobenzimidazole, adenine, pyrazole or 3-amino-5-methylpyrazole is more preferable.
- the pyridine compound is a compound having a hetero 6-membered ring (pyridine ring) containing one nitrogen atom and having aromaticity.
- pyridine ring a hetero 6-membered ring
- Specific examples of the pyridine compound include pyridine, 3-aminopyridine, 4-aminopyridine, 3-hydroxypyridine, 4-hydroxypyridine, 2-acetamide pyridine, 2-cyanopyridine, 2-carboxypyridine, and 4-. Examples include carboxypyridine.
- the pyrazine compound is a compound having aromaticity and having a hetero 6-membered ring (pyrazine ring) containing two nitrogen atoms located at the para position, and the pyrimidine compound has aromaticity and is at the meta position. It is a compound having a hetero 6-membered ring (pyrimidine ring) containing two located nitrogen atoms.
- Examples of the pyrazine compound include pyrazine, 2-methylpyrazine, 2,5-dimethylpyrazine, 2,3,5-trimethylpyrazine, 2,3,5,6-tetramethylpyrazine and 2-ethyl-3-methylpyrazine. , And 2-amino-5-methylpyrazine.
- the pyrimidine compound include pyrimidine, 2-methylpyrimidine, 2-aminopyrimidine, and 4,6-dimethylpyrimidine, with 2-aminopyrimidine being preferred.
- an azole compound or a pyrazine compound is preferable, and an azole compound is more preferable.
- the nitrogen-containing heteroaromatic compound may be used alone or in combination of two or more.
- the content of the nitrogen-containing heteroaromatic compound in the cleaning liquid is not particularly limited, but is preferably 0.01 to 10% by mass with respect to the total mass of the cleaning liquid. More preferably, 0.05 to 5% by mass.
- the content of the nitrogen-containing heteroaromatic compound is 0.1 to 50% by mass with respect to the total mass of the components excluding the solvent in the cleaning liquid. It is preferably 0.5 to 30% by mass, more preferably 0.5 to 30% by mass.
- the reducing agent is a compound having an oxidizing action and having a function of oxidizing OH- ions or dissolved oxygen contained in the cleaning liquid, and is also called an oxygen scavenger.
- the reducing agent functions as an anticorrosive agent that improves the corrosion prevention performance of the cleaning liquid. Therefore, the cleaning liquid preferably contains a reducing agent.
- the reducing agent used in the cleaning liquid is not particularly limited, and examples thereof include ascorbic acid compounds, catechol compounds, hydroxylamine compounds, hydrazide compounds, and reducing sulfur compounds.
- the ascorbic acid compound means at least one selected from the group consisting of ascorbic acid, ascorbic acid derivatives, and salts thereof.
- the ascorbic acid derivative include ascorbic acid phosphate ester and ascorbic acid sulfate ester.
- As the ascorbic acid compound ascorbic acid, ascorbic acid phosphate ester, or ascorbic acid sulfate ester is preferable, and ascorbic acid is more preferable.
- the catechol compound means at least one selected from the group consisting of pyrocatechol (benzene-1,2-diol) and catechol derivatives.
- the catechol derivative means a compound in which at least one substituent is substituted with pyrocatechol.
- a hydroxy group, a carboxy group, a carboxylic acid ester group, a sulfo group, a sulfonic acid ester group, an alkyl group (preferably having 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms), and Aryl groups (preferably phenyl groups) are mentioned.
- the carboxy group and the sulfo group that the catechol derivative has as a substituent may be a salt of a cation. Further, the alkyl group and the aryl group that the catechol derivative has as a substituent may further have a substituent.
- the catechol compound include pyrocatechol, 4-tert-butylcatechol, pyrogallol, gallate, methyl gallate, 1,2,4-benzenetriol, and Tyrone.
- -Hydroxylamine compound- Hydroxylamine compound means at least one selected from the group consisting of hydroxylamine (NH 2 OH), hydroxylamine derivatives, and salts thereof.
- the hydroxylamine derivative means a compound in which at least one organic group is substituted with hydroxylamine (NH 2 OH).
- the salt of hydroxylamine or the hydroxylamine derivative may be an inorganic or organic acid salt of hydroxylamine or the hydroxylamine derivative.
- a salt of an inorganic acid in which at least one non-metal selected from the group consisting of Cl, S, N and P is bonded to hydrogen is preferable, and a hydrochloride or sulfate is preferable. , Or nitrate is more preferred.
- Examples of the hydroxylamine compound include a compound represented by the following formula (1) or a salt thereof.
- R 6 and R 7 each independently represent a hydrogen atom or an organic group.
- an alkyl group having 1 to 6 carbon atoms is preferable.
- the alkyl group having 1 to 6 carbon atoms may be linear, branched or cyclic. Further, it is preferable that at least one of R 6 and R 7 is an organic group (more preferably, an alkyl group having 1 to 6 carbon atoms).
- an ethyl group or an n-propyl group is preferable, and an ethyl group is more preferable.
- hydroxylamine compound examples include hydroxylamine, O-methylhydroxylamine, O-ethylhydroxylamine, N-methylhydroxylamine, N, N-dimethylhydroxylamine, N, O-dimethylhydroxylamine, and N-ethylhydroxylamine.
- N-ethylhydroxylamine, N, N-diethylhydroxylamine (DEHA) or Nn-propylhydroxylamine are preferable, and DEHA is more preferable.
- the hydrazide compound means a compound obtained by substituting a hydroxy group of an acid with a hydrazino group (-NH-NH 2 ) and a derivative thereof (a compound obtained by substituting at least one substituent with a hydrazino group).
- the hydrazide compound may have two or more hydrazino groups. Examples of the hydrazide compound include carboxylic acid hydrazide and sulfonic acid hydrazide, and carbohydrazide (CHZ) is preferable.
- the reducing sulfur compound is not particularly limited as long as it contains a sulfur atom and has a function as a reducing agent.
- mercaptosuccinic acid dithiodiglycerol, bis (2,3-dihydroxypropylthio) ethylene, etc.
- Sodium 3- (2,3-dihydroxypropylthio) -2-methyl-propylsulfonate, 1-thioglycerol, sodium 3-mercapto-1-propanesulfonate, 2-mercaptoethanol, thioglycolic acid, and 3-mercapto -1-Propyl can be mentioned.
- mercapto compound a compound having an SH group
- 1-thioglycerol, 3-mercapto-1-propanesulfonate sodium, 2-mercaptoethanol, 3-mercapto-1-propanol, or thioglycolic acid is more preferable.
- 2-mercaptoethanol, 3-mercapto-1-propanol, or thioglycolic acid is more preferable.
- an ascorbic acid compound or a hydroxylamine compound is preferable, and an ascorbic acid compound is more preferable.
- the cleaning liquid preferably contains two or more kinds of reducing agents in that it is excellent in corrosion prevention performance (particularly corrosion prevention performance for a metal film containing W).
- the content of the reducing agent is not particularly limited, but is preferably 0.01 to 20% by mass, more preferably 0.1 to 5% by mass, based on the total mass of the cleaning liquid.
- the content of the reducing agent is preferably 0.1 to 50% by mass, preferably 0.5 to 30% by mass, based on the total mass of the components excluding the solvent in the cleaning liquid. More preferred.
- these reducing agents commercially available ones may be used, or those synthesized according to a known method may be used.
- Anionic surfactant are compounds that have an anionic hydrophilic group and a hydrophobic group (lipophilic group) in the molecule.
- the anionic surfactant contained in the cleaning liquid examples include a phosphate ester-based surfactant having a phosphate ester group and a phosphonic acid-based surfactant having a phosphonic acid group, each of which has a hydrophilic group (acid group).
- examples thereof include a sulfonic acid-based surfactant having a sulfo group, a carboxylic acid-based surfactant having a carboxy group, and a sulfate ester-based surfactant having a sulfate ester group.
- These anionic surfactants function as anticorrosive agents that not only improve the cleaning performance but also the corrosion prevention performance (particularly the corrosion prevention performance for metal films containing Co and / or Cu). Therefore, the cleaning liquid preferably contains an anionic surfactant.
- phosphoric acid ester-based surfactant examples include a phosphoric acid ester (alkyl ether phosphoric acid ester), a polyoxyalkylene ether phosphoric acid ester, and salts thereof. Phosphoric acid esters and polyoxyalkylene ether phosphoric acids often contain both monoesters and diesters, but monoesters or diesters can be used alone. Examples of the salt of the phosphoric acid ester-based surfactant include a sodium salt, a potassium salt, an ammonium salt, and an organic amine salt.
- the monovalent alkyl group contained in the phosphoric acid ester and the polyoxyalkylene ether phosphoric acid ester is not particularly limited, but an alkyl group having 2 to 24 carbon atoms is preferable, an alkyl group having 6 to 18 carbon atoms is more preferable, and carbon. Alkyl groups of numbers 12-18 are more preferred.
- the divalent alkylene group contained in the polyoxyalkylene ether phosphoric acid ester is not particularly limited, but an alkylene group having 2 to 6 carbon atoms is preferable, and an ethylene group or a 1,2-propanediyl group is more preferable.
- the number of repetitions of the oxyalkylene group in the polyoxyalkylene ether phosphoric acid ester is preferably 1 to 12, more preferably 3 to 10.
- Examples of the phosphoric acid ester-based surfactant include octyl phosphate, lauryl phosphate, tridecyl phosphate, myristyl phosphate, cetyl phosphate, stearyl phosphate, polyoxyethylene octyl ether phosphate, and polyoxyethylene. Lauryl ether phosphate or polyoxyethylene tridecyl ether phosphate is preferred.
- phosphonic acid-based surfactant examples include alkylphosphonic acid and polyvinylphosphonic acid, and for example, aminomethylphosphonic acid described in JP-A-2012-057108 and the like.
- sulfonic acid-based surfactant examples include alkyl sulfonic acid, alkyl benzene sulfonic acid, alkyl naphthalene sulfonic acid, alkyl diphenyl ether disulfonic acid, alkyl methyl taurine, sulfosuccinic acid diester, polyoxyalkylene alkyl ether sulfonic acid, and salts thereof.
- the sulfonic acid-based surfactant include alkyl sulfonic acid, alkyl benzene sulfonic acid, alkyl naphthalene sulfonic acid, alkyl diphenyl ether disulfonic acid, alkyl methyl taurine, sulfosuccinic acid diester, polyoxyalkylene alkyl ether sulfonic acid, and salts thereof.
- the monovalent alkyl group contained in the above-mentioned sulfonic acid-based surfactant is not particularly limited, but an alkyl group having 10 or more carbon atoms is preferable, and an alkyl group having 12 or more carbon atoms is more preferable.
- the upper limit is not particularly limited, but is preferably 24 or less.
- the divalent alkylene group contained in the polyoxyalkylene alkyl ether sulfonic acid is not particularly limited, but an ethylene group or a 1,2-propanediyl group is preferable.
- the number of repetitions of the oxyalkylene group in the polyoxyalkylene alkyl ether sulfonic acid is preferably 1 to 12, more preferably 1 to 6.
- sulfonic acid-based surfactant examples include hexane sulfonic acid, octane sulfonic acid, decane sulfonic acid, dodecane sulfonic acid, toluene sulfonic acid, cumene sulfonic acid, octylbenzene sulfonic acid, dodecylbenzenesulfonic acid (DBSA), and di.
- examples thereof include nitrobenzene sulfonic acid (DNBSA) and laurildodecylphenyl ether disulfonic acid (LDPEDSA).
- a sulfonic acid-based surfactant having an alkyl group having 10 or more carbon atoms is preferable, a sulfonic acid-based surfactant having an alkyl group having 12 or more carbon atoms is more preferable, and DBSA is further preferable.
- carboxylic acid-based surfactant examples include alkylcarboxylic acids, alkylbenzenecarboxylic acids, polyoxyalkylene alkyl ether carboxylic acids, and salts thereof.
- the monovalent alkyl group contained in the above-mentioned carboxylic acid-based surfactant is not particularly limited, but an alkyl group having 7 to 25 carbon atoms is preferable, and an alkyl group having 11 to 17 carbon atoms is more preferable.
- the divalent alkylene group contained in the polyoxyalkylene alkyl ether carboxylic acid is not particularly limited, but an ethylene group or a 1,2-propanediyl group is preferable.
- the number of repetitions of the oxyalkylene group in the polyoxyalkylene alkyl ether carboxylic acid is preferably 1 to 12, more preferably 1 to 6.
- carboxylic acid-based surfactant examples include lauric acid, myristic acid, palmitic acid, stearic acid, polyoxyethylene lauryl ether acetic acid, and polyoxyethylene tridecyl ether acetic acid.
- sulfate ester-based surfactant examples include a sulfate ester (alkyl ether sulfate ester), a polyoxyalkylene ether sulfate ester, and salts thereof.
- the monovalent alkyl group contained in the sulfuric acid ester and the polyoxyalkylene ether sulfuric acid ester is not particularly limited, but an alkyl group having 2 to 24 carbon atoms is preferable, and an alkyl group having 6 to 18 carbon atoms is more preferable.
- the divalent alkylene group contained in the polyoxyalkylene ether sulfate ester is not particularly limited, but an ethylene group or a 1,2-propanediyl group is preferable.
- the number of repetitions of the oxyalkylene group in the polyoxyalkylene ether sulfate ester is preferably 1 to 12, more preferably 1 to 6.
- Specific examples of the sulfate ester-based surfactant include lauryl sulfate ester, myristyl sulfate ester, and polyoxyethylene lauryl ether sulfate ester.
- anionic surfactant examples include a phosphoric acid ester-based surfactant, a sulfonic acid-based surfactant (more preferably, a sulfonic acid-based surfactant having an alkyl group having 12 or more carbon atoms), a phosphonic acid-based surfactant, and the like. And at least one selected from the group consisting of carboxylic acid-based surfactants, preferably phosphoric acid ester-based surfactants, sulfonic acid-based surfactants having an alkyl group having 12 or more carbon atoms, or phosphonic acid-based surfactants. Agents are more preferred.
- the cleaning liquid preferably contains two or more kinds of anionic surfactants in that it is excellent in corrosion prevention performance (particularly corrosion prevention performance for a metal film containing Cu and / or Co).
- the content thereof is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.0% by mass, based on the total mass of the cleaning liquid.
- the content thereof is preferably 0.05 to 50% by mass, preferably 0.5 to 30% by mass, based on the total mass of the components excluding the solvent in the cleaning liquid. Is more preferable.
- these anionic surfactants commercially available ones may be used.
- the cleaning solution may contain a chelating agent.
- the chelating agent used in the cleaning liquid is a compound having a function of chelating with the metal contained in the residue in the cleaning step of the semiconductor substrate. Among them, a compound having two or more functional groups (coordinating groups) that coordinate-bond with a metal ion in the molecule is preferable. In the present specification, the compounds contained in the above-mentioned component A, component B and component C are not included in the chelating agent.
- the cleaning liquid preferably contains a chelating agent because it is excellent in cleaning performance and corrosion prevention performance.
- the chelating agent examples include an organic chelating agent and an inorganic chelating agent.
- the organic chelating agent is a chelating agent composed of an organic compound, and has, for example, a hydroxycarboxylic acid chelating agent, an aliphatic carboxylic acid chelating agent, and at least two nitrogen-containing groups (groups containing a nitrogen atom). Moreover, a compound having no carboxyl group (hereinafter, also referred to as “specific nitrogen-containing chelating agent”) can be mentioned.
- the inorganic chelating agent include condensed phosphoric acid and a salt thereof.
- an organic chelating agent is preferable, and a hydroxycarboxylic acid chelating agent is more preferable.
- hydroxycarboxylic acid-based chelating agent examples include malic acid, citric acid, glycolic acid, gluconic acid, heptonic acid, tartaric acid, and lactic acid, and gluconic acid, glycolic acid, malic acid, tartaric acid, or citric acid is preferable. , Gluconic acid or citric acid are more preferred.
- Examples of the aliphatic carboxylic acid-based chelating agent include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, sebacic acid, and maleic acid, and adipic acid is preferable.
- adipic acid can significantly improve the performance of the cleaning liquid (cleaning performance and corrosion resistance) as compared with other chelating agents.
- the number of carbon chains of the alkylene group is particularly excellent in the relationship with the two carboxy groups, and it is particularly excellent in hydrophilicity and hydrophobicity, and during complex formation with a metal. It is expected to be derived from the formation of a stable ring structure.
- the hydroxycarboxylic acid chelating agent and the aliphatic carboxylic acid chelating agent preferably have a low molecular weight.
- the molecular weight of these chelating agents is preferably 600 or less, more preferably 450 or less, and even more preferably 300 or less.
- the lower limit is not particularly limited, but is preferably 85 or more.
- the number of carbon atoms of the hydroxycarboxylic acid chelating agent and the aliphatic carboxylic acid chelating agent is preferably 15 or less, more preferably 12 or less, and even more preferably 8 or less.
- the lower limit is not particularly limited, but 2 or more is preferable.
- Examples of the specific nitrogen-containing chelating agent include at least one biguanide compound selected from the group consisting of a compound having a biguanide group and a salt thereof.
- the number of biguanide groups contained in the biguanide compound is not particularly limited, and may have a plurality of biguanide groups.
- Examples of the biguanide compound include the compounds described in paragraphs [0034] to [0055] of JP-A-2017-504190, the contents of which are incorporated in the present specification.
- Compounds having a biguanide group include ethylene diviguanide, propylene dibiguanide, tetramethylene dibiguanide, pentamethylene dibiguanide, hexamethylene dibiguanide, heptamethylene dibiguanide, octamethylene dibiguanide, and 1,1'-hexamethylenebis ( 5- (p-chlorophenyl) biguanide) (chlorhexidine), 2- (benzyloxymethyl) pentane-1,5-bis (5-hexylbiguanide), 2- (phenylthiomethyl) pentane-1,5-bis (5) -Phenetyl biguanide), 3- (phenylthio) hexane-1,6-bis (5-hexylbiguanide), 3- (phenylthio) hexane-1,6-bis (5-cyclohexylbiguanide), 3- (benzylthio) hexane- 1,
- condensed phosphoric acid and its salt which are inorganic chelating agents, include pyrophosphoric acid and its salt, metaphosphoric acid and its salt, tripolyphosphoric acid and its salt, and hexametaphosphoric acid and its salt.
- a hydroxycarboxylic acid chelating agent As the chelating agent, a hydroxycarboxylic acid chelating agent, an aliphatic carboxylic acid chelating agent or a biganide compound is preferable, and gluconic acid, glycolic acid, malic acid, tartaric acid, citric acid, adipic acid or chlorhexidine or a salt thereof is more preferable. Gluconic acid, citric acid, malic acid or chlorhexidine or salts thereof are more preferred.
- the chelating agent may be used alone or in combination of two or more.
- the content of the chelating agent in the cleaning liquid is not particularly limited, but the total mass of the cleaning liquid is excellent in corrosion prevention performance (particularly, corrosion prevention performance for metal films containing Cu and / or Co).
- 0.01% by mass or more is preferable, and 0.05% by mass or more is more preferable.
- the upper limit is not particularly limited, but is preferably 3% by mass or less, more preferably 2% by mass or less, based on the total mass of the cleaning liquid.
- the content of the chelating agent is preferably 0.1 to 30% by mass, preferably 0.5 to 20% by mass, based on the total mass of the components excluding the solvent in the cleaning liquid. More preferred.
- the component D one type may be used alone, or two or more types may be used in combination.
- the content of the component D is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and 0.1% by mass with respect to the total mass of the cleaning liquid. % Or more is more preferable.
- the upper limit of the content of the component D is not particularly limited, but is preferably 10.0% by mass or less, more preferably 5.0% by mass or less, still more preferably 3.0% by mass or less, based on the total mass of the cleaning liquid. ..
- the content of the component D is preferably 0.05% by mass or more, more preferably 0.3% by mass or more, based on the total mass of the components excluding the solvent in the cleaning liquid. , 0.5% by mass or more is more preferable.
- the upper limit is not particularly limited, but is preferably 80% by mass or less, more preferably 50% by mass or less, still more preferably 30% by mass or less, based on the total mass of the components excluding the solvent in the cleaning liquid.
- the mass ratio is preferably 200 or less, more preferably 100 or less, still more preferably 20 or less, in that it is excellent in cleaning performance (particularly cleaning performance for a metal film containing Cu and / or Co).
- the lower limit of the mass ratio is not particularly limited, but is preferably 0.1 or more, and more preferably 0.3 or more in that it is excellent in corrosion prevention performance (particularly, corrosion prevention performance for a metal film containing Cu and / or Co). ..
- the cleaning liquid may contain a quaternary ammonium compound.
- the quaternary ammonium compound is not particularly limited as long as it is a compound having a quaternary ammonium cation in which a nitrogen atom is substituted with four hydrocarbon groups (preferably an alkyl group) or a salt thereof.
- Examples of the quaternary ammonium compound include a quaternary ammonium hydroxide, a quaternary ammonium fluoride, a quaternary ammonium bromide, a quaternary ammonium iodide, a quaternary ammonium acetate, and a quaternary ammonium compound. Examples include ammonium carbonate.
- the cleaning liquid preferably contains a quaternary ammonium compound because it is excellent in corrosion prevention performance (particularly, corrosion prevention performance for metal films containing Cu and / or Co).
- quaternary ammonium hydroxide represented by the following formula (2) is preferable.
- R 8 represents an alkyl group which may have a hydroxy group or a phenyl group as a substituent.
- the four R 8 may being the same or different.
- an alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group or an ethyl group is more preferable.
- the alkyl group which may have a hydroxy group or a phenyl group represented by R 8 a methyl group, an ethyl group, a propyl group, a butyl group, a 2-hydroxyethyl group, or a benzyl group is preferable, and a methyl group, An ethyl group, a propyl group, a butyl group, or a 2-hydroxyethyl group is more preferable, and a methyl group, an ethyl group, or a 2-hydroxyethyl group is further preferable.
- quaternary ammonium compound examples include tetramethylammonium hydroxide (TMAH), trimethylethylammonium hydroxide (TMEAH), diethyldimethylammonium hydroxide (DEDH), methyltriethylammonium hydroxide (MTEAH), and tetraethylammonium hydroxide.
- TMAH tetramethylammonium hydroxide
- TAEAH trimethylethylammonium hydroxide
- DEDH diethyldimethylammonium hydroxide
- MTEAH methyltriethylammonium hydroxide
- TMAH tetramethylammonium hydroxide
- TAEAH trimethylethylammonium hydroxide
- DEDH diethyldimethylammonium hydroxide
- MTEAH methyltriethylammonium hydroxide
- tetraethylammonium hydroxide examples include tetramethylammoni
- TEAH Tetrapropyl Ammonium Hydroxide
- TBAH Tetrabutyl Ammonium Hydroxide
- 2-Hydroxyethyl trimethylammonium Hydroxide Colin
- Bis (2-Hydroxyethyl) Dimethylammonium Hydroxide Tri (2-) Examples thereof include hydroxyethyl) methylammonium hydroxide, tetra (2-hydroxyethyl) ammonium hydroxide, benzyltrimethylammonium hydroxide (BTMAH), and cetyltrimethylammonium hydroxide.
- BTMAH benzyltrimethylammonium hydroxide
- cetyltrimethylammonium hydroxide cetyltrimethylammonium hydroxide.
- TMAH TMAH
- TMEAH DEDH
- MTEAH TEAH
- TPAH TBAH
- choline or bis (2-hydroxyethyl) dimethylammonium hydroxide
- MTEAH is more preferable.
- the cleaning liquid preferably contains a quaternary ammonium compound having an asymmetric structure from the viewpoint of excellent corrosion prevention performance (particularly corrosion prevention performance for a metal film containing Cu and / or Co).
- a quaternary ammonium compound "has an asymmetric structure" it means that none of the four hydrocarbon groups substituting for nitrogen atoms are the same.
- the quaternary ammonium compound having an asymmetric structure include TMEAH, DEDHA, MTEAH, choline, and bis (2-hydroxyethyl) dimethylammonium hydroxide, and MTEAH is preferable.
- the quaternary ammonium compound may be used alone or in combination of two or more.
- the cleaning liquid preferably contains two or more kinds of quaternary ammonium compounds in that it is excellent in cleaning performance (particularly cleaning performance for a metal film containing Cu and / or Co).
- the content thereof is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, based on the total mass of the cleaning liquid, in that the cleaning performance is more excellent. 0.2% by mass or more is more preferable.
- the upper limit of the content of the quaternary ammonium compound is not particularly limited, but 10% by mass or less is preferable from the viewpoint of suppressing deterioration of cleaning performance due to aggregation of residue particles and / or readsorption of residue in the cleaning step. 5% by mass or less is more preferable, and 3% by mass or less is further preferable.
- the content thereof is preferably 0.2 to 30% by mass, preferably 0.5 to 15% by mass, based on the total mass of the components excluding the solvent in the cleaning liquid. Is more preferable.
- the cleaning liquid may contain a surfactant other than the anionic surfactant.
- the other surfactant is not particularly limited as long as it is a compound other than an anionic surfactant having a hydrophilic group and a hydrophobic group (lipophilic group) in the molecule, and is, for example, a cationic surfactant or a nonionic surfactant.
- Surfactants and amphoteric surfactants can be mentioned.
- Surfactants often have hydrophobic groups selected from aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and combinations thereof.
- the hydrophobic group contained in the surfactant is not particularly limited, but when the hydrophobic group contains an aromatic hydrocarbon group, the number of carbon atoms is preferably 6 or more, and more preferably 10 or more.
- the number of carbon atoms is preferably 10 or more, more preferably 12 or more, and the number of carbon atoms is 12. It is more preferably 16 or more.
- the upper limit of the number of carbon atoms of the hydrophobic group is not particularly limited, but is preferably 20 or less, and more preferably 18 or less.
- Cationic surfactants include, for example, primary to tertiary alkylamine salts (eg, monostearylammonium chloride, distearylammonium chloride, tristearylammonium chloride, etc.), and modified aliphatic polyamines (eg, for example. (Polyethylene polyamine, etc.) can be mentioned.
- primary to tertiary alkylamine salts eg, monostearylammonium chloride, distearylammonium chloride, tristearylammonium chloride, etc.
- modified aliphatic polyamines eg, for example. (Polyethylene polyamine, etc.) can be mentioned.
- Nonionic surfactant examples include polyoxyalkylene alkyl ether (for example, polyoxyethylene stearyl ether, etc.), polyoxyalkylene alkenyl ether (for example, polyoxyethylene oleyl ether, etc.), polyoxyethylene alkyl phenyl ether (for example, polyoxyethylene alkyl phenyl ether, etc.).
- Polyoxyethylene nonylphenyl ether, etc. Polyoxyethylene nonylphenyl ether, etc.
- Polyoxyalkylene glycol eg, polyoxypropylene polyoxyethylene glycol, etc.
- Polyoxyalkylene monoalchelate monoalkyl fatty acid ester polyoxyalkylene
- polyoxyethylene monosteer Rate
- polyoxyethylene monoalchelates such as polyoxyethylene monoolate
- polyoxyalkylene dialchelates dialkyl fatty acid ester polyoxyalkylene
- Oxyethylene dial chelate bispolyoxyalkylene alkylamide (eg, bispolyoxyethylene stearylamide, etc.), sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylamine, glycerin fatty acid ester, oxyethylene oxypropylene block
- Examples include copolymers, acetylene glycol-based surfactants, and acetylene-based polyoxyethylene oxide.
- amphoteric surfactant examples include carboxybetaine (eg, alkyl-N, N-dimethylaminoacetic acid betaine and alkyl-N, N-dihydroxyethylaminoacetic acid betaine, etc.) and sulfobetaine (eg, alkyl-N, N- (Dimethylsulfoethyleneammonium betaine, etc.) and imidazolinium betaine (eg, 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine, etc.).
- carboxybetaine eg, alkyl-N, N-dimethylaminoacetic acid betaine and alkyl-N, N-dihydroxyethylaminoacetic acid betaine, etc.
- sulfobetaine eg, alkyl-N, N- (Dimethylsulfoethyleneammonium betaine, etc.
- imidazolinium betaine eg, 2-alkyl-
- surfactant examples include paragraphs [0092] to [0090] of JP2015-158662, paragraphs [0045] to [0046] of JP2012-151273, and paragraphs of JP2009-147389.
- the compounds described in [0014] to [0020] can also be incorporated, and the contents thereof are incorporated in the present specification.
- the cleaning liquid may contain additives other than the above-mentioned components, if necessary.
- additives include pH regulators, anticorrosive agents (excluding the components contained in component D), polymers, fluorine compounds, and organic solvents.
- the cleaning solution may contain a pH regulator to adjust and maintain the pH of the cleaning solution.
- Examples of the pH adjuster include basic compounds and acidic compounds other than the above components.
- Examples of the basic compound include a basic organic compound and a basic inorganic compound.
- the basic organic compound is a basic organic compound different from the above-mentioned components.
- Examples of basic organic compounds include amine oxides, nitros, nitroso, oximes, ketooximes, aldoximes, lactams, isocyanide compounds, and ureas.
- Examples of the basic inorganic compound include alkali metal hydroxides, alkaline earth metal hydroxides, and ammonia.
- Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide, and cesium hydroxide.
- Examples of the alkaline earth metal hydroxide include calcium hydroxide, strontium hydroxide, and barium hydroxide.
- the compound contained as the above-mentioned component A, component B, component C and / or component D may also serve as a basic compound for raising the pH of the cleaning liquid.
- these basic compounds commercially available ones may be used, or those appropriately synthesized by a known method may be used.
- Examples of acidic compounds include inorganic acids and organic acids.
- Examples of the inorganic acid include hydrochloric acid, sulfuric acid, sulfurous acid, nitric acid, nitrite, phosphoric acid, boric acid, and hexafluorinated phosphoric acid.
- salts of inorganic acids may be used, and examples thereof include ammonium salts of inorganic acids, and more specifically, ammonium chloride, ammonium sulfate, ammonium sulfite, ammonium nitrate, ammonium nitrite, ammonium phosphate, and ammonium borate. , And ammonium hexafluoride phosphate.
- As the inorganic acid phosphoric acid or phosphate is preferable, and phosphoric acid is more preferable.
- the organic acid is an organic compound having an acidic functional group and showing acidity (pH is less than 7.0) in an aqueous solution, and is contained in both the above-mentioned chelating agent and the above-mentioned anionic surfactant. It is a compound that cannot be used.
- the organic acid include lower (1 to 4 carbon atoms) aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, and butyric acid.
- the acidic compound a salt of the acidic compound may be used as long as it becomes an acid or an acid ion (anion) in an aqueous solution.
- the chelating agent and / or the anionic surfactant contained in the cleaning liquid may also serve as an acidic compound for lowering the pH of the cleaning liquid.
- the acidic compound a commercially available compound may be used, or a compound appropriately synthesized by a known method may be used.
- the pH adjuster one type may be used alone, or two or more types may be used in combination.
- the cleaning solution contains a pH adjuster
- the content thereof is selected according to the type and amount of other components and the pH of the target cleaning solution, but is 0.01 to 3 with respect to the total mass of the cleaning solution. It is preferably by mass, more preferably 0.05 to 1% by mass.
- the cleaning liquid contains a pH adjuster
- the content thereof is selected according to the type and amount of other components and the pH of the target cleaning liquid, but the total mass of the components excluding the solvent in the cleaning liquid. With respect to this, 0.05 to 10% by mass is preferable, and 0.2 to 5% by mass is more preferable.
- the cleaning liquid may contain other anticorrosive agents other than the above-mentioned components.
- Other anticorrosive agents include, for example, saccharides such as fructose, glucose and ribose, polyol compounds such as ethylene glycol, propylene glycol and glycerin, polyacrylic acid, polymaleic acid, and polycarboxylic acid compounds such as copolymers thereof.
- Examples of the polymer include water-soluble polymers described in paragraphs [0043] to [0047] of JP-A-2016-171294, the contents of which are incorporated in the present specification.
- Examples of the fluorine compound include the compounds described in paragraphs [0013] to [0015] of JP-A-2005-150236, the contents of which are incorporated in the present specification.
- As the organic solvent any known organic solvent can be used, but hydrophilic organic solvents such as alcohol and ketone are preferable.
- the organic solvent may be used alone or in combination of two or more.
- the amounts of the polymer, the fluorine compound, and the organic solvent used are not particularly limited, and may be appropriately set as long as the effects of the present invention are not impaired.
- the content of each of the above components in the washing solution is determined by a gas chromatography-mass spectrometry (GC-MS) method or a liquid chromatography-mass spectrometry (LC-MS) method. , And known methods such as ion-exchange chromatography (IC).
- GC-MS gas chromatography-mass spectrometry
- LC-MS liquid chromatography-mass spectrometry
- known methods such as ion-exchange chromatography (IC).
- the cleaning solution is preferably alkaline. That is, the pH of the cleaning liquid is preferably more than 7.0 at 25 ° C.
- the pH of the cleaning liquid is more preferably 8.0 or more at 25 ° C., and further more than 8.5 in that it is excellent in cleaning performance and corrosion prevention performance (particularly corrosion prevention performance for metal films containing Co and / or Cu). It is preferable, and 9.0 or more is particularly preferable.
- the upper limit of the pH of the cleaning liquid is not particularly limited, but is preferably 12.0 or less at 25 ° C., and is less than 11.5 in that it is superior in corrosion prevention performance (particularly corrosion prevention performance for metal films containing W and / or Cu).
- the pH of the cleaning solution can be adjusted by using the above-mentioned pH adjuster and a component having the function of a pH adjuster such as the above-mentioned component A, component B, component C, component D, and quaternary ammonium compound. Just do it.
- the pH of the cleaning solution can be measured by a method based on JIS Z8802-1984 using a known pH meter.
- the cleaning liquid contains the metal (metal elements of Fe, Co, Na, K, Cu, Mg, Mn, Li, Al, Cr, Ni, Zn, Sn and Ag) contained as impurities in the liquid (as an ion concentration).
- the metal is preferably 5 mass ppm or less, and more preferably 1 mass ppm or less.
- the metal content thereof should be lower than 1 mass ppm, that is, mass ppb order or less. It is preferably 100 mass ppb or less, and most preferably less than 10 mass ppb.
- the lower limit is not particularly limited, but 0 is preferable.
- distillation and purification treatment such as filtration using an ion exchange resin or a filter are performed at the stage of the raw material used in the production of the cleaning liquid or the stage after the production of the cleaning liquid.
- a container for accommodating the raw material or the produced cleaning liquid a container with less elution of impurities, which will be described later, may be used.
- a fluorinated resin lining to the wetted portion of the member such as the inner wall of the pipe so that the metal component does not elute from the member such as the pipe during the production of the cleaning liquid.
- the cleaning liquid may contain coarse particles, but the content thereof is preferably low.
- the coarse particles mean particles having a diameter (particle size) of 0.4 ⁇ m or more when the shape of the particles is regarded as a sphere.
- the content of coarse particles in the cleaning liquid is preferably 1000 or less, and more preferably 500 or less, per 1 mL of the cleaning liquid.
- the lower limit is not particularly limited, but 0 can be mentioned. Further, it is more preferable that the content of particles having a particle size of 0.4 ⁇ m or more measured by the above measuring method is not more than the detection limit.
- the coarse particles contained in the cleaning liquid include particles such as dust, dust, organic solids, and inorganic solids contained as impurities in the raw material, and dust, dust, organic solids, and dust, dust, organic solids, which are brought in as contaminants during the preparation of the cleaning liquid. Particles such as inorganic solids that finally exist as particles without being dissolved in the cleaning liquid fall under this category.
- the content of coarse particles present in the cleaning liquid can be measured in the liquid phase by using a commercially available measuring device in a light scattering type submerged particle measuring method using a laser as a light source. Examples of the method for removing coarse particles include purification treatment such as filtering described later.
- the cleaning liquid may be a kit in which the raw material is divided into a plurality of parts.
- Examples of the method using the cleaning liquid as a kit include an embodiment in which a liquid composition containing component A and component B is prepared as the first liquid and a liquid composition containing component C and other components is prepared as the second liquid. Be done.
- the cleaning liquid can be produced by a known method. Hereinafter, the method for producing the cleaning liquid will be described in detail.
- the method for preparing the cleaning liquid is not particularly limited, and for example, the cleaning liquid can be produced by mixing the above-mentioned components.
- the order and / or timing of mixing each of the above-mentioned components is not particularly limited, and for example, component A, component B and component C, and component D and fourth as optional components are placed in a container containing purified pure water. Examples thereof include a method of preparing the mixture by sequentially adding the quaternary ammonium compound, stirring and mixing, and adding a pH adjusting agent to adjust the pH of the mixed solution. Further, when water and each component are added to the container, they may be added all at once or divided into a plurality of times.
- the stirring device and stirring method used for preparing the cleaning liquid are not particularly limited, and a known device as a stirring machine or a disperser may be used.
- the stirrer include an industrial mixer, a portable stirrer, a mechanical stirrer, and a magnetic stirrer.
- Dispersers include, for example, industrial dispersers, homogenizers, ultrasonic dispersers, and bead mills.
- Mixing of each component in the preparation step of the cleaning liquid, the purification treatment described later, and storage of the produced cleaning liquid are preferably performed at 40 ° C. or lower, and more preferably at 30 ° C. or lower. Further, 5 ° C. or higher is preferable, and 10 ° C. or higher is more preferable.
- the purification treatment is not particularly limited, and examples thereof include known methods such as distillation, ion exchange, and filtration.
- the degree of purification is not particularly limited, but it is preferable to purify until the purity of the raw material is 99% by mass or more, and it is more preferable to purify until the purity of the raw material is 99.9% by mass or more.
- Specific methods of the purification treatment include, for example, a method of passing the raw material through an ion exchange resin or an RO membrane (Reverse Osmosis Membrane), distillation of the raw material, and filtering described later.
- a plurality of the above-mentioned purification methods may be combined and carried out.
- the raw material is subjected to primary purification by passing it through an RO membrane, and then passed through a purification device made of a cation exchange resin, an anion exchange resin, or a mixed bed type ion exchange resin. You may.
- the purification treatment may be carried out a plurality of times.
- the filter used for filtering is not particularly limited as long as it has been conventionally used for filtering purposes.
- fluororesins such as polytetrafluoroethylene (PTFE) and tetrafluoroethylene perfluoroalkyl vinyl ether copolymer (PFA), polyamide resins such as nylon, and polyolefin resins such as polyethylene and polypropylene (PP) (high density).
- a filter consisting of can be mentioned.
- a material selected from the group consisting of polyethylene, polypropylene (including high-density polypropylene), fluororesin (including PTFE and PFA), and polyamide-based resin (including nylon) is preferable, and a fluororesin filter is preferable. Is more preferable.
- the critical surface tension of the filter is preferably 70 to 95 mN / m, more preferably 75 to 85 mN / m.
- the value of the critical surface tension of the filter is the nominal value of the manufacturer.
- the pore diameter of the filter is preferably 2 to 20 nm, more preferably 2 to 15 nm. Within this range, it is possible to reliably remove fine foreign substances such as impurities and agglomerates contained in the raw material while suppressing filtration clogging.
- the nominal value of the filter manufacturer can be referred to.
- Filtering may be performed only once or twice or more. When filtering is performed twice or more, the filters used may be the same or different.
- filtering is preferably performed at room temperature (25 ° C.) or lower, more preferably 23 ° C. or lower, and even more preferably 20 ° C. or lower. Further, 0 ° C. or higher is preferable, 5 ° C. or higher is more preferable, and 10 ° C. or higher is further preferable.
- the cleaning liquid (including the form of the kit or the diluted liquid described later) can be filled in an arbitrary container and stored, transported, and used as long as problems such as corrosiveness do not occur.
- a container having a high degree of cleanliness inside the container and suppressing elution of impurities from the inner wall of the container accommodating portion into each liquid is preferable.
- examples of such a container include various containers commercially available as a container for a semiconductor cleaning liquid, and examples thereof include a "clean bottle” series manufactured by Aicello Chemical Corporation and a "pure bottle” manufactured by Kodama Resin Industry Co., Ltd. However, it is not limited to these.
- the wetted portion with each liquid such as the inner wall of the accommodating portion is formed of a fluororesin (perfluororesin) or a metal subjected to rust prevention and metal elution prevention treatment. Fluororesin is preferred.
- the inner wall of the container is made of one or more resins selected from the group consisting of polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin, or a resin different from this, or stainless steel, hasteroi, inconel, monel, etc. It is preferably formed from a metal that has been subjected to rust and metal elution prevention treatment.
- a fluororesin (perfluororesin) is preferable.
- a problem of elution of ethylene or propylene oligomer occurs as compared with a container whose inner wall is a polyethylene resin, a polypropylene resin, or a polyethylene-polypropylene resin.
- Specific examples of such a container whose inner wall is a fluororesin include a FluoroPure PFA composite drum manufactured by Entegris.
- the container described on page 4 of Japanese Patent Publication No. 3-502677, page 3 of International Publication No. 2004/016526, and pages 9 and 16 of International Publication No. 99/046309. Can also be used.
- quartz and an electropolished metal material are also preferably used for the inner wall of the container.
- the metal material used for producing the electropolished metal material contains at least one selected from the group consisting of chromium and nickel, and the total content of chromium and nickel is 25 mass with respect to the total mass of the metal material. It is preferably a metal material in excess of%. Examples of such metal materials include stainless steel and nickel-chromium alloys.
- the total content of chromium and nickel in the metal material is more preferably 30% by mass or more with respect to the total mass of the metal material.
- the upper limit of the total content of chromium and nickel in the metal material is not particularly limited, but is preferably 90% by mass or less.
- the method for electrolytically polishing a metal material is not particularly limited, and a known method can be used.
- a known method can be used.
- the methods described in paragraphs [0011]-[0014] of JP2015-227501 and paragraphs [0036]-[0042] of JP2008-264929 can be used.
- the inside of these containers is cleaned before being filled with the cleaning liquid.
- the liquid used for cleaning preferably has a reduced amount of metal impurities in the liquid.
- the cleaning liquid may be bottling, transported, and stored in a container such as a gallon bottle or a coated bottle after production.
- the inside of the container may be replaced with an inert gas (nitrogen, argon, etc.) having a purity of 99.99995% by volume or more.
- an inert gas nitrogen, argon, etc.
- a gas having a low water content is preferable.
- the temperature may be normal temperature, but the temperature may be controlled in the range of ⁇ 20 ° C. to 20 ° C. in order to prevent deterioration.
- the clean room preferably meets the 14644-1 clean room standard. It is preferable to satisfy any one of ISO (International Organization for Standardization) class 1, ISO class 2, ISO class 3, and ISO class 4, more preferably ISO class 1 or ISO class 2, and ISO class 1 is satisfied. Is more preferable.
- ISO International Organization for Standardization
- the above-mentioned cleaning liquid is preferably used for cleaning the semiconductor substrate after undergoing a dilution step of diluting with a diluent such as water.
- the dilution ratio of the cleaning liquid in the dilution step may be appropriately adjusted according to the type and content of each component and the semiconductor substrate to be cleaned, but the ratio of the diluted cleaning liquid to the cleaning liquid before dilution is 10 by volume. It is preferably from 10000 times to 10000 times, more preferably 20 to 3000 times, still more preferably 50 to 1000 times.
- the cleaning liquid is preferably diluted with water because it is superior in defect suppression performance.
- the change in pH (difference between the pH of the cleaning solution before dilution and the pH of the diluted cleaning solution) before and after dilution is preferably 1.0 or less, more preferably 0.8 or less, still more preferably 0.5 or less.
- the pH of the diluted cleaning solution is preferably more than 7.0, more preferably 7.5 or more, and even more preferably 8.0 or more at 25 ° C.
- the upper limit of the pH of the diluted washing solution is preferably 13.0 or less, more preferably 12.5 or less, and even more preferably 12.0 or less at 25 ° C.
- the content of component A in the diluted cleaning solution is preferably 0.00003% by mass or more, preferably 0.00005% by mass, based on the total mass of the diluted cleaning solution, in that the cleaning performance (particularly the cleaning performance for a metal film containing Co) is more excellent. It is more preferably mass% or more, and further preferably 0.0001 mass% or more.
- the upper limit is not particularly limited, it is preferably 0.02% by mass or less, preferably 0.01% by mass, based on the total mass of the diluted cleaning liquid, in that it is excellent in corrosion prevention performance (particularly, cleaning performance for a metal film containing Cu or Co).
- the following is more preferable, 0.008% by mass or less is further preferable, and 0.005% by mass or less is particularly preferable.
- the content of component B in the diluted cleaning solution is not particularly limited, but is preferably 0.00005% by mass or more, preferably 0.00008 mass by mass, based on the total mass of the diluted cleaning solution in that it is superior in cleaning performance to a metal film containing Cu. % Or more is more preferable, and 0.0001% by mass or more is further preferable.
- the upper limit is not particularly limited, but it is preferably 0.02% by mass or less, preferably 0.015% by mass or less, based on the total mass of the diluted cleaning liquid, in that it is excellent in corrosion prevention performance (particularly, corrosion prevention performance for metal films containing Cu). Is more preferable, and 0.012% by mass or less is further preferable.
- the content of component C in the diluted cleaning solution is not particularly limited, but is preferably 0.0003 to 0.3% by mass, more preferably 0.0005 to 0.15% by mass, and 0, based on the total mass of the diluted cleaning solution. More preferably, it is .005 to 0.12% by mass.
- the water content in the diluted cleaning solution may be component A, component B, component C, and the balance of the above optional components.
- the water content is, for example, preferably 90% by mass or more, more preferably 99.3% by mass or more, further preferably 99.6% by mass or more, and 99.85% by mass or more, based on the total mass of the diluted cleaning liquid. Is particularly preferable.
- the upper limit is not particularly limited, but is preferably 99.99% by mass or less, more preferably 99.95% by mass or less, based on the total mass of the diluted cleaning liquid.
- the content of the component D is not particularly limited, but 0.0001% by mass or more is preferable, 0.0005% by mass or more is more preferable, and 0. 001% by mass or more is more preferable.
- the upper limit of the content of the component D is not particularly limited, but is preferably 0.1% by mass or less, more preferably 0.05% by mass or less, and further preferably 0.03% by mass or less, based on the total mass of the diluted cleaning liquid. preferable.
- the diluted cleaning solution contains a nitrogen-containing heteroaromatic compound
- the content of the nitrogen-containing heteroaromatic compound in the diluted cleaning solution is not particularly limited, but is 0.0001 to 0.1 with respect to the total mass of the diluted cleaning solution.
- the diluted cleaning solution contains a reducing agent
- the content of the reducing agent is not particularly limited, but is preferably 0.0001 to 0.2% by mass, preferably 0.001 to 0.05% by mass, based on the total mass of the diluted cleaning solution. Is more preferable.
- the diluted cleaning solution contains an anionic surfactant
- the content thereof is preferably 0.0001 to 0.05% by mass, more preferably 0.0005 to 0.02% by mass, based on the total mass of the diluted cleaning solution. ..
- the content of the chelating agent in the diluted cleaning solution is not particularly limited, but is 0.
- 0001% by mass or more is preferable, and 0.0005% by mass or more is more preferable.
- the upper limit is not particularly limited, but is preferably 0.03% by mass or less, more preferably 0.02% by mass or less, based on the total mass of the diluted cleaning liquid.
- the content thereof is preferably 0.0005% by mass or more, more preferably 0.001% by mass or more, based on the total mass of the diluted cleaning solution in terms of being superior in cleaning performance. It is preferable, and 0.002% by mass or more is more preferable.
- the upper limit of the content of the quaternary ammonium compound is not particularly limited, but is 0.1% by mass or less in that the deterioration of the cleaning performance due to the aggregation of the residue particles and / or the readsorption of the residue in the cleaning step is suppressed.
- 0.05% by mass or less is more preferable, and 0.03% by mass or less is further preferable.
- the diluted cleaning solution contains a pH adjuster, the content thereof is selected according to the type and amount of other components and the pH of the desired diluted cleaning solution, but is 0. It is preferably 0001 to 0.03% by mass, more preferably 0.0005 to 0.01% by mass.
- the specific method of the dilution step of diluting the cleaning liquid is not particularly limited, and may be performed according to the above-mentioned liquid preparation step of the cleaning liquid.
- the stirring device and the stirring method used in the dilution step are also not particularly limited, and the known stirring device mentioned in the above-mentioned cleaning liquid preparation step may be used.
- the purification treatment is not particularly limited, and examples thereof include an ion component reduction treatment using an ion exchange resin or an RO membrane and foreign matter removal using filtering, which are described as the purification treatment for the cleaning liquid described above. It is preferable to carry out the treatment of.
- the cleaning liquid is used in a cleaning process for cleaning a semiconductor substrate that has been subjected to chemical mechanical polishing (CMP) treatment. Further, the cleaning liquid can be used for cleaning the semiconductor substrate in the semiconductor substrate manufacturing process, and can also be used as a composition for buffing treatment described later. As described above, a diluted cleaning solution obtained by diluting the cleaning solution may be used for cleaning the semiconductor substrate.
- CMP chemical mechanical polishing
- Examples of the object to be cleaned by the cleaning liquid include a semiconductor substrate having a metal-containing substance.
- the term "on the semiconductor substrate” in the present specification includes, for example, the front and back surfaces, the side surfaces, and the inside of the groove of the semiconductor substrate.
- the metal-containing material on the semiconductor substrate includes not only the case where the metal-containing material is directly on the surface of the semiconductor substrate but also the case where the metal-containing material is present on the semiconductor substrate via another layer.
- the metals contained in the metal-containing material include, for example, Cu (copper), Co (cobalt), W (tungsten), Ti (titanium), Ta (tantalum), Ru (ruthenium), Cr (chromium), Hf (hafnium). , Os (osmium), Pt (platinum), Ni (nickel), Mn (manganese), Zr (zirconium), Mo (molybdenum), La (lantern), and Ir (iridium) at least selected from the group.
- Cu copper
- Co cobalt
- W tungsten
- Ti titanium
- Ta tantalum
- Ru ruthenium
- Cr chromium
- Hf hafnium
- Os osmium
- Pt platinum
- Ni nickel
- Mn manganese
- Zr zirconium
- Mo molybdenum
- La lantern
- Ir iridium
- the metal-containing material may be a substance containing a metal (metal atom), for example, a simple substance of the metal M, an alloy containing the metal M, an oxide of the metal M, a nitride of the metal M, and a metal M. Acid nitrides can be mentioned. Moreover, the metal-containing material may be a mixture containing two or more of these compounds.
- the oxide, nitride, and oxynitride may be a composite oxide containing a metal, a composite nitride, or a composite oxynitride.
- the content of the metal atom in the metal-containing material is preferably 10% by mass or more, more preferably 30% by mass or more, still more preferably 50% by mass or more, based on the total mass of the metal-containing material.
- the upper limit is 100% by mass because the metal-containing material may be the metal itself.
- the semiconductor substrate preferably has a metal M-containing material containing a metal M, and may have a metal-containing material containing at least one metal selected from the group consisting of Cu, Co, W, Ti, Ta and Ru. More preferably, it has a metal-containing material containing at least one metal selected from the group consisting of Cu, Co, Ti, Ta, Ru, and W.
- the semiconductor substrate to be cleaned by the cleaning liquid is not particularly limited, and examples thereof include a substrate having a metal wiring film, a barrier metal, and an insulating film on the surface of the wafer constituting the semiconductor substrate.
- wafers constituting a semiconductor substrate include a silicon (Si) wafer, a silicon carbide (SiC) wafer, a wafer made of a silicon-based material such as a resin-based wafer containing silicon (glass epoxy wafer), and gallium phosphorus (GaP). Wafers, gallium arsenic (GaAs) wafers, and indium phosphorus (InP) wafers can be mentioned. Silicon wafers include n-type silicon wafers in which a silicon wafer is doped with pentavalent atoms (for example, phosphorus (P), arsenic (As), antimony (Sb), etc.), and silicon wafers are trivalent atoms (for example,).
- pentavalent atoms for example, phosphorus (P), arsenic (As), antimony (Sb), etc.
- silicon wafers are trivalent atoms (for example,).
- the silicon of the silicon wafer may be, for example, amorphous silicon, single crystal silicon, polycrystalline silicon, or polysilicon.
- the cleaning liquid is useful for wafers made of silicon-based materials such as silicon wafers, silicon carbide wafers, and resin-based wafers (glass epoxy wafers) containing silicon.
- the semiconductor substrate may have an insulating film on the above-mentioned wafer.
- the insulating film is a silicon oxide film (e.g., silicon dioxide (SiO 2) film, and tetraethyl orthosilicate (Si (OC 2 H 5) 4) film (TEOS film), etc.), a silicon nitride film (e.g., silicon nitride (Si 3 N 4), and silicon carbonitride (SiNC), etc.), as well as low dielectric constant (low-k) film (e.g., carbon-doped silicon oxide (SiOC) film, and a silicon carbide (SiC) film or the like ).
- silicon oxide film e.g., silicon dioxide (SiO 2) film, and tetraethyl orthosilicate (Si (OC 2 H 5) 4) film (TEOS film), etc.
- TEOS film tetraethyl orthosilicate
- Si silicon nitride
- the semiconductor substrate preferably has a metal film containing at least one selected from the group consisting of copper and cobalt. It is also preferable that the semiconductor substrate has a metal film containing tungsten.
- the copper-containing film examples include a wiring film made of only metallic copper (copper wiring film) and a wiring film made of an alloy of metallic copper and another metal (copper alloy wiring film).
- Specific examples of the copper alloy wiring film include one or more metals and copper selected from aluminum (Al), titanium (Ti), chromium (Cr), manganese (Mn), tantalum (Ta), and tungsten (W).
- cobalt-containing film examples include a metal film composed of only metallic cobalt (cobalt metal film) and a metal film made of an alloy composed of metallic cobalt and another metal (cobalt alloy metal).
- cobalt alloy metal film examples include titanium (Ti), chromium (Cr), iron (Fe), nickel (Ni), molybdenum (Mo), palladium (Pd), tantalum (Ta), and tungsten (W).
- cobalt alloy metal film examples include titanium (Ti), chromium (Cr), iron (Fe), nickel (Ni), molybdenum (Mo), palladium (Pd), tantalum (Ta), and tungsten (W).
- examples thereof include a metal film made of an alloy composed of one or more kinds of metals selected from the above and cobalt.
- cobalt-titanium alloy metal film (CoTi alloy metal film), cobalt-chromium alloy metal film (CoCr alloy metal film), cobalt-iron alloy metal film (CoFe alloy metal film), cobalt-nickel alloy metal.
- Film CoNi alloy metal film
- cobalt-molybdenum alloy metal film (CoMo alloy metal film)
- cobalt-palladium alloy metal film (CoPd alloy metal film)
- cobalt-tantal alloy metal film CoTa alloy metal film
- cobalt- Examples thereof include a tungsten alloy metal film (CoW alloy metal film).
- the cleaning liquid is useful for substrates having a cobalt-containing film.
- the cobalt metal film is often used as a wiring film
- the cobalt alloy metal film is often used as a barrier metal.
- the cleaning liquid has at least a copper-containing wiring film and a metal film (cobalt barrier metal) which is composed of only metal cobalt and is a barrier metal of the copper-containing wiring film on the upper part of the wafer constituting the semiconductor substrate. It may be preferable to use it for cleaning a substrate in which a copper-containing wiring film and a cobalt barrier metal are in contact with each other on the surface of the substrate.
- a metal film cobalt barrier metal
- the tungsten-containing film examples include a metal film composed of only tungsten (tungsten metal film) and a metal film made of an alloy composed of tungsten and another metal (tungsten alloy metal film). Can be mentioned. Specific examples of the tungsten alloy metal film include a tungsten-titanium alloy metal film (WTi alloy metal film) and a tungsten-cobalt alloy metal film (WCo alloy metal film). Tungsten-containing films are often used as barrier metals.
- the method for forming the insulating film, the copper-containing wiring film, the cobalt-containing film, and the tungsten-containing film on the wafer constituting the semiconductor substrate is not particularly limited as long as it is a known method used in this field.
- a method for forming the insulating film for example, a silicon oxide film is formed by heat-treating a wafer constituting a semiconductor substrate in the presence of oxygen gas, and then silane and ammonia gas are introduced to form a chemical vapor deposition. Examples thereof include a method of forming a silicon nitride film by a vapor deposition (CVD) method.
- a method for forming the copper-containing wiring film, the cobalt-containing film, and the tungsten-containing film for example, a circuit is formed on a wafer having the above-mentioned insulating film by a known method such as a resist, and then plating and a CVD method or the like are performed.
- a method for forming a copper-containing wiring film, a cobalt-containing film, and a tungsten-containing film can be mentioned.
- the CMP treatment is, for example, a treatment for flattening the surface of a substrate having a metal wiring film, a barrier metal, and an insulating film by a combined action of chemical action using a polishing slurry containing polishing fine particles (abrasive grains) and mechanical polishing. is there.
- abrasive grains for example, silica and alumina
- a polished metal wiring film for example, a polished metal wiring film, and metal impurities (metal residues) derived from the barrier metal are present. Impurities may remain.
- the semiconductor substrate subjected to the CMP treatment is subjected to a cleaning treatment for removing these impurities from the surface. Served.
- Specific examples of the semiconductor substrate subjected to the CMP treatment include the Journal of the Precision Engineering Society Vol. 84, No. 3.
- the substrate subjected to the CMP treatment according to 2018 can be mentioned, but is not limited thereto.
- the surface of the semiconductor substrate which is the object to be cleaned by the cleaning liquid, may be buffed after being subjected to CMP treatment.
- the buffing treatment is a treatment for reducing impurities on the surface of a semiconductor substrate by using a polishing pad. Specifically, the surface of the semiconductor substrate subjected to the CMP treatment is brought into contact with the polishing pad, and the semiconductor substrate and the polishing pad are relatively slid while supplying the buffing composition to the contact portion. As a result, impurities on the surface of the semiconductor substrate are removed by the frictional force of the polishing pad and the chemical action of the buffing composition.
- a known buffing composition can be appropriately used depending on the type of the semiconductor substrate and the type and amount of impurities to be removed.
- the components contained in the buffing composition are not particularly limited, and examples thereof include water-soluble polymers such as polyvinyl alcohol, water as a dispersion medium, and acids such as nitric acid.
- the polishing apparatus and polishing conditions used in the buffing treatment can be appropriately selected from known apparatus and conditions according to the type of semiconductor substrate and the object to be removed. Examples of the buffing treatment include the treatments described in paragraphs [805] to [0088] of International Publication No. 2017/169539, the contents of which are incorporated in the present specification.
- the method for cleaning the semiconductor substrate is not particularly limited as long as it includes a cleaning step of cleaning the semiconductor substrate subjected to the CMP treatment using the above-mentioned cleaning liquid.
- the method for cleaning the semiconductor substrate preferably includes a step of applying the diluted cleaning liquid obtained in the above dilution step to the semiconductor substrate subjected to the CMP treatment for cleaning.
- the cleaning step of cleaning the semiconductor substrate with the cleaning liquid is not particularly limited as long as it is a known method performed on the CMP-treated semiconductor substrate, and the cleaning member such as a brush is transferred to the semiconductor while supplying the cleaning liquid to the semiconductor substrate.
- Brush scrub cleaning that physically contacts the surface of the substrate to remove residues, immersion type that immerses the semiconductor substrate in the cleaning liquid, spin (drop) type that drops the cleaning liquid while rotating the semiconductor substrate, and spraying the cleaning liquid
- a known method performed in this field, such as a spray type may be appropriately adopted.
- the immersion type cleaning it is preferable to perform ultrasonic treatment on the cleaning liquid in which the semiconductor substrate is immersed because impurities remaining on the surface of the semiconductor substrate can be further reduced.
- the cleaning step may be performed only once or twice or more. When washing twice or more, the same method may be repeated, or different methods may be combined.
- the single-wafer method is a method of processing semiconductor substrates one by one
- the batch method is a method of processing a plurality of semiconductor substrates at the same time.
- the temperature of the cleaning liquid used for cleaning the semiconductor substrate is not particularly limited as long as it is the temperature used in this field. Cleaning is often performed at room temperature (25 ° C.), but the temperature can be arbitrarily selected in order to improve the cleaning property and / or suppress damage to the members.
- the temperature of the cleaning liquid is preferably 10 to 60 ° C, more preferably 15 to 50 ° C.
- the cleaning time in cleaning a semiconductor substrate cannot be unequivocally determined because it depends on the type and content of the components contained in the cleaning liquid, but practically, it is preferably 10 seconds to 2 minutes, and 20 seconds to 1 minute 30 minutes. Seconds are more preferred, and 30 seconds to 1 minute are even more preferred.
- the supply amount (supply rate) of the cleaning liquid in the semiconductor substrate cleaning step is not particularly limited, but is preferably 50 to 5000 mL / min, more preferably 500 to 2000 mL / min.
- a mechanical stirring method may be used in order to further improve the cleaning ability of the cleaning liquid.
- the mechanical stirring method include a method of circulating the cleaning liquid on the semiconductor substrate, a method of flowing or spraying the cleaning liquid on the semiconductor substrate, and a method of stirring the cleaning liquid by ultrasonic waves or megasonic.
- a step of rinsing the semiconductor substrate with a solvent to clean it (hereinafter referred to as a “rinse step”) may be performed.
- the rinsing step is continuously performed after the cleaning step of the semiconductor substrate, and is preferably a rinsing step using a rinsing solvent (rinsing solution) for 5 seconds to 5 minutes.
- the rinsing step may be performed using the mechanical stirring method described above.
- rinsing solvent examples include water (preferably De Ionize (DI) water), methanol, ethanol, isopropyl alcohol, N-methylpyrrolidinone, ⁇ -butyrolactone, dimethyl sulfoxide, ethyl lactate, and propylene glycol monomethyl ether acetate.
- DI De Ionize
- methanol preferably methanol
- ethanol isopropyl alcohol
- N-methylpyrrolidinone ethyl lactate
- propylene glycol monomethyl ether acetate propylene glycol monomethyl ether acetate.
- an aqueous rinse solution having a pH of more than 8 diluted aqueous ammonium hydroxide or the like
- the above-mentioned method of bringing the cleaning liquid into contact with the semiconductor substrate can be similarly applied.
- a drying step of drying the semiconductor substrate may be performed.
- the drying method is not particularly limited, for example, a spin drying method, a method of flowing a dry gas over a semiconductor substrate, a method of heating the substrate by a heating means such as a hot plate or an infrared lamp, a marangoni drying method, and a rotagoni. Drying methods, IPA (isopropyl alcohol) drying methods, and any combination thereof can be mentioned.
- the pH of the cleaning solution was measured at 25 ° C. using a pH meter (manufactured by HORIBA, Ltd., model "F-74") in accordance with JIS Z8802-1984. Further, in the production of the cleaning liquids of Examples and Comparative Examples, the handling of the container, the preparation, filling, storage and analytical measurement of the cleaning liquid were all carried out in a clean room at a level satisfying ISO class 2 or less. In order to improve the measurement accuracy, when measuring the metal content of the cleaning liquid that is below the detection limit by normal measurement, the cleaning liquid is concentrated to 1/100 in terms of volume, and the measurement is performed before concentration. The content was calculated by converting it to the concentration of the solution of.
- MTEAH Methyltriethylammonium hydroxide
- TEAH Tetraethylammonium hydroxide
- a pH adjuster either potassium hydroxide (KOH) or sulfuric acid (H 2 SO 4 ), and commercially available ultrapure water (Fujifilm Wako Pure Chemical Industries, Ltd.) Co., Ltd.) was used.
- Example 1 a method for producing the cleaning liquid will be described by taking Example 1 as an example.
- glycine, DTPA (diethylenetriaminepentaacetic acid), AMP (2-amino-2-methyl-1-propanol), 2-aminopyrimidine, and phosphate HLP are listed in Tables 1 and 2 below.
- a pH adjuster was added so that the pH of the prepared cleaning solution was 10.5.
- the cleaning liquid of Example 1 was obtained by sufficiently stirring the obtained mixed liquid with a stirrer.
- Example 1 According to the production method of Example 1, the cleaning solutions of Examples 2 to 45 and Comparative Examples 1 to 8 having the compositions shown in Tables 1 and 2, respectively, were produced.
- the "Amount (%)” column indicates the content (unit: mass%) of each component with respect to the total mass of the cleaning liquid.
- “* 1" in the “Amount” column of the "pH adjuster” indicates that either H 2 SO 4 or KOH was added in an amount that makes the pH of the prepared cleaning solution the value in the "pH” column. means.
- the numerical value in the "ratio 1" column is the content of component B (content of component B / content of component A) with respect to the content of component A (the total content when a plurality of them are used. The same shall apply hereinafter). Shows the mass ratio.
- the numerical value in the "ratio 2" column is the content of component C with respect to the sum of the content of component A and the content of component B (content of component C / (content of component A + content of component B)). Shows the mass ratio of.
- the numerical value in the "ratio 3" column is the content of the component D with respect to the sum of the content of the component A and the content of the component B (content of the component D / (content of the component A + content of the component B)). Shows the mass ratio of.
- the numerical value in the "pH” column indicates the pH of the cleaning solution measured by the above pH meter at 25 ° C.
- the metal content of the cleaning liquids produced in each Example and each Comparative Example was measured.
- the metal content was measured using an Agilent 8800 triple quadrupole ICP-MS (for semiconductor analysis, option # 200) under the following measurement conditions.
- metal particles and metal ions were not distinguished and they were totaled. When two or more kinds of metals were detected, the total content of two or more kinds of metals was determined.
- the measurement results of the metal content are shown in the "metal content (ppb)" column of Tables 1 and 2 (unit: mass ppb). “ ⁇ 10” in Tables 1 and 2 indicates that the metal content in the cleaning liquid was less than 10 mass ppb with respect to the total mass of the cleaning liquid.
- the cleaning performance (residue removal performance) when the metal film subjected to chemical mechanical polishing was cleaned using the cleaning liquid produced by the above method was evaluated.
- 1 mL of the cleaning solution of each Example and each Comparative Example was separated and diluted 100-fold by volume with ultrapure water to prepare a sample of the diluted cleaning solution.
- a wafer (8 inches in diameter) having a metal film made of copper, tungsten or cobalt on the surface was polished using a FREX300S-II (polishing device, manufactured by Ebara Corporation).
- Wafers having a metal film made of copper on the surface were polished using CSL9044C and BSL8176C (trade names, both manufactured by FUJIFILM Planar Solutions) as polishing liquids.
- a wafer having a metal film made of cobalt on its surface was polished using CSL5340C and CSL5250C (trade names, both manufactured by FUJIFILM Planar Solutions) as polishing liquids.
- Wafers having a metal film made of tungsten on the surface were polished using only W-2000 (trade name, manufactured by Cabot Corporation).
- the polishing pressure was 2.0 psi, and the supply rate of the polishing liquid was 0.28 mL / (minute ⁇ cm 2 ).
- the polishing time was 60 seconds. Then, the polished wafer was washed over 30 seconds using a sample of each diluted washing solution adjusted to room temperature (23 ° C.), and then dried.
- the content of copper, tungsten or cobalt in each diluted cleaning solution was measured before and after the immersion treatment.
- the corrosion rate per unit time (unit: ⁇ / min) was calculated from the obtained measurement results.
- the corrosion prevention performance of the cleaning liquid was evaluated according to the following evaluation criteria. The results are shown in Tables 1 and 2. The lower the corrosion rate, the better the corrosion prevention performance of the cleaning liquid.
- Corrosion rate is less than 0.5 ⁇ / min
- B Corrosion rate is 0.5 ⁇ / min or more and less than 1.0 ⁇ / min
- C Corrosion rate is 1.0 ⁇ / min or more and 3.0 ⁇ Less than / min
- D Corrosion rate is 3.0 ⁇ / min or more
- the cleaning liquid of the present invention is excellent in cleaning performance and corrosion prevention performance for metal films containing copper and metal films containing cobalt.
- component B contained glycine, histidine, cysteine or alanine, it was confirmed that the cleaning performance was superior (comparison of Examples 7 and 10 to 15).
- the content of component B was 0.005% by mass or more with respect to the total mass of the cleaning liquid, it was confirmed that the cleaning performance for the metal film containing Cu was superior (comparison between Example 22 and Example 23). ..
- the content of the component B was 1.5% by mass or less with respect to the total mass of the cleaning liquid, it was confirmed that the corrosion prevention performance for the metal film containing Cu was superior (comparison between Example 25 and Example 26). ).
- the cleaning liquid contains an azole compound or a pyrazine compound as the component D (nitrogen-containing heteroaromatic compound), it is superior in corrosion prevention performance to the metal film (Examples 7 and 31 to 33 and 35). comparison).
- the cleaning liquid contains a chelating agent as the component D, it is superior in corrosion prevention performance to the metal film (comparison between Example 36 and Examples 37 to 39, etc.). It was confirmed that when the cleaning liquid contains a reducing agent as the component D, it is superior in corrosion prevention performance to the metal film containing Cu (comparison between Example 36 and Example 42). It was confirmed that when the cleaning liquid contains two or more kinds of reducing agents as the component D, it is superior in the corrosion prevention performance for the metal film containing W (comparison between Example 42 and Example 43).
- Example 7 of Table 1 Even if a compound selected from the following compound group C is used as the component C instead of AMP, the same cleaning performance and corrosion prevention performance as in Example 7 can be obtained. can get. Further, in the cleaning liquid having the composition shown in Example 40 of Table 2, when a compound selected from the following compound group D is used as the chelating agent in the component D instead of citric acid, or the anionic compound in the component D. Even when a phosphonic acid-based surfactant is used as the surfactant instead of the hostene HLP, the same cleaning performance and corrosion prevention performance as in Example 40 can be obtained. The same cleaning performance and corrosion prevention performance as in Example 7 can be obtained.
- Compound Group C Monoethanolamine, 2- (methylamino) -2-methyl-1-propanol, diethanolamine, diethylene glycolamine, trishydroxymethylaminomethane, piperazine, N- (2-aminoethyl) piperazine, 1,4- Bis (2-hydroxyethyl) piperazine, 1,4-bis (2-aminoethyl) piperazine, and 1,4-bis (3-aminopropyl) piperazine.
- Compound Group D Glycolic acid, malic acid, and tartaric acid.
- the buffed wafer was washed over 30 seconds using a sample of the washing liquid of each example adjusted to room temperature (23 ° C.), and then dried.
- the cleaning performance and corrosion prevention performance of the cleaning liquid were evaluated on the polished surface of the obtained wafer according to the above evaluation test method, it was confirmed that the polished surface had the same evaluation results as the cleaning liquid of each of the above examples.
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Abstract
Description
ドライエッチング工程を経た基板には、ドライエッチング残渣物(例えば、メタルハードマスクに由来するチタン系金属等の金属成分、又はフォトレジスト膜に由来する有機成分)が残存することがある。
これらの残渣物は、配線間を短絡し、半導体の電気的な特性に影響を及ぼし得ることから、半導体基板の表面からこれらの残渣物を除去する洗浄工程が行われることが多い。
化学機械研磨処理が施された半導体基板用の洗浄液であって、カルボキシル基を1つ有するアミノ酸である成分Aと、アミノポリカルボン酸及びポリホスホン酸からなる群より選択される少なくとも1種である成分Bと、脂肪族アミンである成分C(ただし、上記成分A、上記アミノポリカルボン酸、及び、第4級アンモニウム化合物は除く)とを含み、上記成分Aの含有量に対する上記成分Bの含有量の質量比が0.2~10であり、上記成分Aの含有量と上記成分Bの含有量との和に対する上記成分Cの含有量の質量比が5~100である、洗浄液。
〔2〕
上記成分Aが、グリシン、ヒスチジン、システイン、アルギニン、メチオニン、サルコシン及びアラニンからなる群より選択される少なくとも1種を含む、〔1〕に記載の洗浄液。
〔3〕
上記成分Bが、ジエチレントリアミン五酢酸、エチレンジアミン四酢酸、トランス-1,2-ジアミノシクロヘキサン四酢酸、ニトリロトリス(メチレンホスホン酸)及びエチレンジアミンテトラ(メチレンホスホン酸)からなる群より選択される少なくとも1種を含む、〔1〕又は〔2〕に記載の洗浄液。
〔4〕
上記成分Cが、アミノアルコールを含む、〔1〕~〔3〕のいずれかに記載の洗浄液。
〔5〕
含窒素へテロ芳香族化合物、還元剤、アニオン性界面活性剤、並びに、キレート剤(ただし、上記成分A、上記成分B及び上記成分Cに含まれる化合物は除く)からなる群より選択される少なくとも1種である成分Dを更に含む、〔1〕~〔4〕のいずれかに記載の洗浄液。
〔6〕
上記成分Aの含有量と上記成分Bの含有量との和に対する上記成分Dの含有量の質量比が0.1~20である、〔5〕に記載の洗浄液。
〔7〕
第4級アンモニウムカチオンを有する化合物又はその塩である第4級アンモニウム化合物を更に含む、〔1〕~〔6〕のいずれかに記載の洗浄液。
〔8〕
上記第4級アンモニウム化合物が有する上記第4級アンモニウムカチオンが非対称構造を有する、〔7〕に記載の洗浄液。
〔9〕
2種以上の上記第4級アンモニウム化合物を含む、〔7〕又は〔8〕に記載の洗浄液。
〔10〕
2種以上の還元剤を更に含む、〔1〕~〔9〕のいずれかに記載の洗浄液。
〔11〕
上記洗浄液のpHが、25℃において8.0~12.0である、〔1〕~〔10〕のいずれかに記載の洗浄液。
〔12〕
上記半導体基板が、銅及びコバルトからなる群より選択される少なくとも1種を含む金属膜を有する、〔1〕~〔11〕のいずれかに記載の洗浄液。
〔13〕
上記半導体基板が、タングステンを含む金属膜を有する、〔1〕~〔12〕のいずれかに記載の洗浄液。
〔14〕
〔1〕~〔13〕のいずれかに記載の洗浄液を、化学機械研磨処理が施された半導体基板に適用して洗浄する工程を含む、半導体基板の洗浄方法。
本明細書において、「~」を用いて表される数値範囲は、「~」の前後に記載される数値を下限値及び上限値として含む範囲を意味する。
本明細書において、「ppm」は「parts-per-million(10-6)」を意味し、「ppb」は「parts-per-billion(10-9)」を意味する。
本明細書に記載の化合物において、特に限定が無い場合は、異性体(原子数が同じであるが構造が異なる化合物)、光学異性体、及び同位体が含まれていてもよい。また、異性体及び同位体は、1種のみが含まれていてもよいし、複数種含まれていてもよい。
なお、洗浄液の洗浄対象及び本発明の効果に関して、「半導体基板が銅を含む金属膜及びコバルトを含む金属膜を有する」との記載は、銅を含む金属膜とコバルトを含む金属膜が同一の金属膜である場合(即ち、単一の金属膜が銅とコバルトの両者を含む場合)と、両者が異なる金属膜である場合のいずれも意味する。
以下、洗浄液に含まれる各成分について、説明する。
洗浄液は、カルボキシル基を1つ有するアミノ酸である成分Aを含む。
成分Aは、分子内に1つのカルボキシル基と1つ以上のアミノ基とを有する化合物であれば特に制限されない。
成分Aとしては、例えば、グリシン、セリン、α-アラニン(2-アミノプロピオン酸)、β-アラニン(3-アミノプロピオン酸)、リジン、ロイシン、イソロイシン、システイン、メチオニン、エチオニン、トレオニン、トリプトファン、チロシン、バリン、ヒスチジン、ヒスチジン誘導体、アスパラギン、グルタミン、アルギニン、プロリン、フェニルアラニン、特開2016-086094号公報の段落[0021]~[0023]に記載の化合物、及びこれらの塩が挙げられる。なお、ヒスチジン誘導体としては、特開2015-165561号公報、及び、特開2015-165562号公報等に記載の化合物が援用でき、これらの内容は本明細書に組み込まれる。また、塩としては、ナトリウム塩、及びカリウム塩等のアルカリ金属塩、アンモニウム塩、炭酸塩、並びに酢酸塩が挙げられる。
成分Aは、低分子量であることが好ましい。具体的には、成分Aの分子量は、600以下が好ましく、450以下がより好ましく、300以下が更に好ましい。下限は特に制限されず、70以上が好ましい。
また、成分Aの炭素数は、15以下が好ましく、12以下がより好ましく、8以下が更に好ましい。下限は特に制限されず、1以上が好ましい。
化合物のCo2+に対する反応速度(溶媒交換速度)は、クライオスタッドにて冷却し、分光測定器の連続測定によりピーク吸収の増減を追跡することにより実施できる。例えば、液体窒素温度下(77K)で、波長400~700nmに現れる分光ピークを追跡することによって、測定できる。なお、ここでの反応速度は23℃での反応速度であるため、測定温度から室温温度への換算を行う。
洗浄液における成分Aの含有量は、洗浄性能(特にCoを含む金属膜に対する洗浄性能)がより優れる点で、洗浄液の全質量に対して、0.003質量%以上が好ましく、0.005質量%以上がより好ましく、0.01質量%以上が更に好ましい。上限は特に制限されないが、腐食防止性能(特にCu又はCoを含む金属膜に対する洗浄性能)により優れる点で、洗浄液の全質量に対して2.0質量%以下が好ましく、1.0質量%以下がより好ましく、0.8質量%以下が更に好ましく、0.5質量%以下が特に好ましい。
また、成分Aの含有量は、洗浄液中の溶剤を除いた成分の合計質量に対して、0.01質量%以上が好ましく、0.02質量%以上がより好ましく、0.05質量%以上が更に好ましい。上限は特に制限されないが、洗浄液中の溶剤を除いた成分の合計質量に対して、15.0質量%以下が好ましく、10.0質量%以下がより好ましく、8.0質量%以下が更に好ましい。
なお、本明細書において、「洗浄液中の溶剤を除いた成分の合計質量」とは、溶剤以外の洗浄液に含まれる全ての成分の含有量の合計を意味する。また、単なる「溶剤」との用語は、水及び有機溶剤の両者を含む。
洗浄液は、アミノポリカルボン酸及びポリホスホン酸からなる群より選択される少なくとも1種である成分Bを含む。
アミノポリカルボン酸は、分子内に1つ以上のアミノ基と2つ以上のカルボキシル基とを有する化合物である。ポリホスホン酸は、分子内に2つ以上のホスホン酸基を有する化合物である。
アミノポリカルボン酸は、分子内に配位基として1つ以上のアミノ基と2つ以上のカルボキシ基を有する化合物である。
アミノポリカルボン酸としては、例えば、アスパラギン酸、グルタミン酸、ブチレンジアミン四酢酸、ジエチレントリアミン五酢酸(DTPA)、エチレンジアミンテトラプロピオン酸、トリエチレンテトラミン六酢酸、1,3-ジアミノ-2-ヒドロキシプロパン-N,N,N’,N’-四酢酸、プロピレンジアミン四酢酸、エチレンジアミン四酢酸(EDTA)、トランス-1,2-ジアミノシクロヘキサン四酢酸(CyDTA)、エチレンジアミン二酢酸、エチレンジアミンジプロピオン酸、1,6-ヘキサメチレン-ジアミン-N,N,N’,N’-四酢酸、トリエチレンテトラミン-N,N,N’,N”,N’”,N”’-六酢酸(TTHA)、N,N-ビス(2-ヒドロキシベンジル)エチレンジアミン-N,N-二酢酸、ジアミノプロパン四酢酸、1,4,7,10-テトラアザシクロドデカン-四酢酸、ジアミノプロパノール四酢酸、(ヒドロキシエチル)エチレンジアミン三酢酸、及びイミノジ酢酸(IDA)が挙げられる。
また、アミノポリカルボン酸の炭素数は、15以下が好ましく、12以下がより好ましい。下限は特に制限されず、4以上が好ましく、6以上がより好ましい。
アミノポリカルボン酸としては、洗浄性能(特にCuを含む金属膜に対する洗浄性能)がより優れる点で、DTPA、EDTA又はCyDTAが好ましく、DTPA又はEDTAがより好ましい。
ポリホスホン酸は、分子内に2つ以上のホスホン酸基を有する化合物である。
ポリホスホン酸としては、例えば、下記式(P1)、式(P2)及び式(P3)で表される化合物が挙げられる。
式(P1)におけるR1としては、炭素数1~6のアルキル基が好ましく、メチル基、エチル基、n-プロピル基、又はイソプロピル基がより好ましい。
なお、本明細書に記載するアルキル基の具体例において、n-はnormal-体を表す。
式(P1)におけるXとしては、ヒドロキシ基が好ましい。
R2で表されるアルキレン基としては、炭素数1~6の直鎖状又は分岐鎖状のアルキレン基が好ましく、炭素数1~4の直鎖状又は分岐鎖状のアルキレン基がより好ましく、エチレン基が更に好ましい。
式(P2)及び(P4)においてR3で表されるアルキレン基としては、炭素数1~10の直鎖状もしくは分岐鎖状のアルキレン基が挙げられ、炭素数1~4の直鎖状又は分岐鎖状のアルキレン基が好ましく、メチレン基又はエチレン基がより好ましく、メチレン基が更に好ましい。
式(P2)及び(P4)におけるQとしては、-R3-PO3H2が好ましい。
式(P2)におけるYとしては、-R3-PO3H2又は式(P4)で表される基が好ましく、式(P4)で表される基がより好ましい。
式(P3)におけるnとしては、1又は2が好ましい。
Z1~Z5で表されるホスホン酸基を有するアルキル基におけるホスホン酸基の数としては、1つ又は2つが好ましく、1つがより好ましい。
Z1~Z5で表されるホスホン酸基を有するアルキル基としては、例えば、炭素数1~4の直鎖状又は分岐鎖状であって、ホスホン酸基を1つ又は2つ有するアルキル基が挙げられ、(モノ)ホスホノメチル基、又は(モノ)ホスホノエチル基が好ましく、(モノ)ホスホノメチル基がより好ましい。
式(P3)におけるZ1~Z5としては、Z1~Z4及びn個のZ5のすべてが、上記のホスホン酸基を有するアルキル基であることが好ましい。
また、ポリホスホン酸の炭素数は、15以下が好ましく、12以下がより好ましく、8以下が更に好ましい。下限は特に制限されず、3以上が好ましい。
ポリホスホン酸としては、上記の式(P1)、(P2)及び(P3)で表されるポリホスホン酸のそれぞれにおいて好適な具体例として挙げた化合物が好ましく、洗浄性能(特にCuを含む金属膜に対する洗浄性能)がより優れる点で、NTPO又はEDTPOがより好ましく、EDTPOが更に好ましい。
成分Bとしては、洗浄性能(特にCuを含む金属膜に対する洗浄性能)がより優れる点で、ジエチレントリアミン五酢酸(DTPA)、エチレンジアミン四酢酸(EDTA)、トランス-1,2-ジアミノシクロヘキサン四酢酸(CyDTA)、ニトリロトリス(メチレンホスホン酸)(NTPO)、又はエチレンジアミンテトラ(メチレンホスホン酸)(EDTPO)が好ましく、DTPA、EDTA、CyDTA又はEDTPOがより好ましく、DTPA、EDTA又はEDTPOが更に好ましい。
化合物の第1錯生成定数Km1は、下記の公知の方法によって求められる。即ち、金属と配位子とのキレート生成反応における結合定数(錯生成定数)は、下記式(1)で求められる。
洗浄液における成分Bの含有量は、特に制限されないが、Cuを含む金属膜に対する洗浄性能により優れる点で、洗浄液の全質量に対して、0.005質量%以上が好ましく、0.008質量%以上がより好ましく、0.01質量%以上が更に好ましい。上限は特に制限されないが、腐食防止性能(特にCuを含む金属膜に対する腐食防止性能)により優れる点で、洗浄液の全質量に対して2.0質量%以下が好ましく、1.5質量%以下がより好ましく、1.2質量%以下が更に好ましい。
また、成分Bの含有量は、洗浄液中の溶剤を除いた成分の合計質量に対して、0.02質量%以上が好ましく、0.05質量%以上がより好ましく、0.1質量%以上が更に好ましい。上限は特に制限されないが、洗浄液中の溶剤を除いた成分の合計質量に対して、20.0質量%以下が好ましく、15.0質量%以下がより好ましく、10.0質量%以下が更に好ましい。
洗浄液は、成分Cとして脂肪族アミンを含む。ただし、成分Cとしての脂肪族アミンには、成分A、成分Bとしてのアミノポリカルボン酸、及び第4級アンモニウム化合物は含まれない。
第1級アミン、第2級アミン及び第3級アミンからなる群より選択される少なくとも1種(以下「第1級~第3級アミン」ともいう。)の塩としては、例えば、Cl、S、N及びPからなる群より選択される少なくとも1種の非金属が水素と結合してなる無機酸の塩が挙げられ、塩酸塩、硫酸塩、又は硝酸塩が好ましい。
成分Cとしては、例えば、アミノアルコール、脂環式アミン、並びに、アミノアルコール及び脂環式アミン以外の脂肪族モノアミン化合物及び脂肪族ポリアミン化合物が挙げられる。
アミノアルコールは、第1級~第3級アミンのうち、分子内に少なくとも1つのヒドロキシルアルキル基を更に有する化合物である。アミノアルコールは、第1級~第3級アミノ基のいずれを有していてもよいが、第1級アミノ基を有することが好ましい。
なかでも、AMP、N-MAMP、MEA、DEA、Tris又はDEGAが好ましく、AMPがより好ましい。
脂環式アミン化合物は、環を構成する原子の少なくとも1つが窒素原子である非芳香性の複素環を有する化合物であれば、特に制限されない。
脂環式アミン化合物としては、例えば、ピペラジン化合物、及び環状アミジン化合物が挙げられる。
ピペラジン化合物は、ピペラジン環上に置換基を有してもよい。そのような置換基としては、例えば、ヒドロキシ基、ヒドロキシ基を有していてもよい炭素数1~4のアルキル基、及び炭素数6~10のアリール基が挙げられる。
環状アミジン化合物が有する上記のヘテロ環の環員数は、特に制限されないが、5又は6個が好ましく、6個がより好ましい。
環状アミジン化合物としては、例えば、ジアザビシクロウンデセン(1,8-ジアザビシクロ[5.4.0]ウンデカ-7-エン:DBU)、ジアザビシクロノネン(1,5-ジアザビシクロ[4.3.0]ノナ-5-エン:DBN)、3,4,6,7,8,9,10,11-オクタヒドロ-2H-ピリミド[1.2-a]アゾシン、3,4,6,7,8,9-ヘキサヒドロ-2H-ピリド[1.2-a]ピリミジン、2,5,6,7-テトラヒドロ-3H-ピロロ[1.2-a]イミダゾール、3-エチル-2,3,4,6,7,8,9,10-オクタヒドロピリミド[1.2-a]アゼピン、及びクレアチニンが挙げられる。
アミノアルコール及び脂環式アミン以外の脂肪族モノアミン化合物としては、例えば、下記式(a)で表される化合物(以下「化合物(a)」とも記載する)が挙げられる。
NHxR(3-x) (a)
式中、Rは炭素数1~3のアルキル基を表し、xは0~2の整数を表す。
炭素数1~3のアルキル基としては、メチル基、エチル基、n-プロピル基、及びイソプロピル基が挙げられ、エチル基又はn-プロピル基が好ましい。
アミノアルコール及び脂環式アミン以外の脂肪族ポリアミン化合物としては、例えば、エチレンジアミン(EDA)、1,3-プロパンジアミン(PDA)、1,2-プロパンジアミン、1,3-ブタンジアミン、及び1,4-ブタンジアミン等のアルキレンジアミン、並びに、ジエチレントリアミン(DETA)、トリエチレンテトラミン(TETA)、ビス(アミノプロピル)エチレンジアミン(BAPEDA)及びテトラエチレンペンタミン等のポリアルキルポリアミンが挙げられる。
このようなアミン化合物としては、1つ以上の第1級~第3級アミノ基と1つ以上のヒドロキシ基を有するアミノアルコール、2つ以上の第1級~第3級アミノ基を有する脂肪族ポリアミン化合物、及び脂環式アミン化合物のうち2つ以上の親水性基を有する化合物が挙げられる。
成分Cが有する親水性基の総数の上限は特に制限されないが、5以下が好ましく、4以下がより好ましい。
洗浄液における成分Cの含有量は、特に制限されないが、洗浄液の全質量に対して、0.03~30質量%が好ましく、0.05~15質量%がより好ましく、0.5~12質量%が更に好ましい。
また、成分Cの含有量は、洗浄液中の溶剤を除いた成分の合計質量に対して、3.0~99.0質量%が好ましく、5.0~98.0質量%がより好ましく、20.0~95.0質量%が更に好ましい。
洗浄液は、溶剤として水を含むことが好ましい。
洗浄液に使用される水の種類は、半導体基板に悪影響を及ぼさないものであれば特に制限されず、蒸留水、脱イオン水、及び純水(超純水)が使用できる。不純物をほとんど含まず、半導体基板の製造工程における半導体基板への影響がより少ない点で、純水が好ましい。
洗浄液における水の含有量は、成分A、成分B、成分C、及び、後述する任意成分の残部であればよい。水の含有量は、例えば、洗浄液の全質量に対して、1質量%以上が好ましく、30質量%以上がより好ましく、60質量%以上が更に好ましく、85質量%以上が特に好ましい。上限値は特に制限されないが、洗浄液の全質量に対して、99質量%以下が好ましく、95質量%以下がより好ましい。
洗浄液は、上述した成分以外に、他の任意成分を含んでいてもよい。以下、任意成分について説明する。
洗浄液は、含窒素ヘテロ芳香族化合物、還元剤、アニオン性界面活性剤、並びにキレート剤(ただし、成分A、成分B及び成分Cに含まれる化合物は除く)からなる群より選択される少なくとも1種である成分Dを含んでいてもよい。
含窒素へテロ芳香族化合物は、環を構成する原子の少なくとも1つが窒素原子であるヘテロ芳香環(含窒素ヘテロ芳香環)を有する化合物であれば、特に制限されない。含窒素へテロ芳香族化合物は、洗浄液の腐食防止性能を向上させる防食剤として機能する。そのため、洗浄液は含窒素へテロ芳香族化合物を含むことが好ましい。
含窒素へテロ芳香族化合物としては、特に制限されないが、例えば、アゾール化合物、ピリジン化合物、ピラジン化合物、及び、ピリミジン化合物が挙げられる。
また、アゾール化合物は、ヘテロ5員環上に置換基を有してもよい。そのような置換基としては、例えば、ヒドロキシ基、カルボキシ基、メルカプト基、アミノ基、アミノ基を有していてもよい炭素数1~4のアルキル基、及び2-イミダゾリル基が挙げられる。
アゾール化合物としては、例えば、イミダゾール化合物、ピラゾール化合物、チアゾール化合物、トリアゾール化合物、及びテトラゾール化合物が挙げられる。
ピリジン化合物としては、具体的には、ピリジン、3-アミノピリジン、4-アミノピリジン、3-ヒドロキシピリジン、4-ヒドロキシピリジン、2-アセトアミドピリジン、2-シアノピリジン、2-カルボキシピリジン、及び4-カルボキシピリジンが挙げられる。
ピラジン化合物としては、例えば、ピラジン、2-メチルピラジン、2,5-ジメチルピラジン、2,3,5-トリメチルピラジン、2,3,5,6-テトラメチルピラジン、2-エチル-3-メチルピラジン、及び2-アミノ-5-メチルピラジンが挙げられる。
ピリミジン化合物としては、例えば、ピリミジン、2-メチルピリミジン、2-アミノピリミジン、及び4,6-ジメチルピリミジンが挙げられ、2-アミノピリミジンが好ましい。
洗浄液が含窒素へテロ芳香族化合物を含む場合、洗浄液における含窒素へテロ芳香族化合物の含有量は、特に制限されないが、洗浄液の全質量に対して、0.01~10質量%が好ましく、0.05~5質量%がより好ましい。
また、洗浄液が含窒素へテロ芳香族化合物を含む場合、含窒素へテロ芳香族化合物の含有量は、洗浄液中の溶剤を除いた成分の合計質量に対して、0.1~50質量%が好ましく、0.5~30質量%がより好ましい。
還元剤は、酸化作用を有し、洗浄液に含まれるOH-イオン又は溶存酸素を酸化する機能を有する化合物であり、脱酸素剤とも称される。還元剤は、洗浄液の腐食防止性能を向上させる防食剤として機能する。そのため、洗浄液は還元剤を含むことが好ましい。
洗浄液に用いられる還元剤としては、特に制限されないが、例えば、アスコルビン酸化合物、カテコール化合物、ヒドロキシルアミン化合物、ヒドラジド化合物、及び還元性硫黄化合物が挙げられる。
アスコルビン酸化合物は、アスコルビン酸、アスコルビン酸誘導体、及びそれらの塩からなる群より選択される少なくとも1種を意味する。
アスコルビン酸誘導体としては、例えば、アスコルビン酸リン酸エステル、及びアスコルビン酸硫酸エステルが挙げられる。
アスコルビン酸化合物としては、アスコルビン酸、アスコルビン酸リン酸エステル、又はアスコルビン酸硫酸エステルが好ましく、アスコルビン酸がより好ましい。
カテコール化合物は、ピロカテコール(ベンゼン-1,2-ジオール)、及びカテコール誘導体からなる群より選択される少なくとも1種を意味する。
カテコール誘導体とは、ピロカテコールに少なくとも1つの置換基が置換されてなる化合物を意味する。カテコール誘導体が有する置換基としては、ヒドロキシ基、カルボキシ基、カルボン酸エステル基、スルホ基、スルホン酸エステル基、アルキル基(炭素数1~6が好ましく、炭素数1~4がより好ましい)、及びアリール基(フェニル基が好ましい)が挙げられる。カテコール誘導体が置換基として有するカルボキシ基、及びスルホ基は、カチオンの塩であってもよい。また、カテコール誘導体が置換基として有するアルキル基、及びアリール基は、更に置換基を有していてもよい。
カテコール化合物としては、例えば、ピロカテコール、4-tert-ブチルカテコール、ピロガロール、没食子酸、没食子酸メチル、1,2,4-ベンゼントリオール、及びタイロンが挙げられる。
ヒドロキシルアミン化合物は、ヒドロキシルアミン(NH2OH)、ヒドロキシルアミン誘導体、及びそれらの塩からなる群より選択される少なくとも1種を意味する。また、ヒドロキシルアミン誘導体とは、ヒドロキシルアミン(NH2OH)に少なくとも1つの有機基が置換されてなる化合物を意味する。
ヒドロキシルアミン又はヒドロキシルアミン誘導体の塩は、ヒドロキシルアミン又はヒドロキシルアミン誘導体の無機酸塩又は有機酸塩であってもよい。ヒドロキシルアミン又はヒドロキシルアミン誘導体の塩としては、Cl、S、N及びPからなる群より選択される少なくとも1種の非金属が水素と結合してなる無機酸の塩が好ましく、塩酸塩、硫酸塩、又は硝酸塩がより好ましい。
また、R6及びR7の少なくとも一方が有機基(より好ましくは炭素数1~6のアルキル基)であることが好ましい。
炭素数1~6のアルキル基としては、エチル基又はn-プロピル基が好ましく、エチル基がより好ましい。
なかでも、N-エチルヒドロキシルアミン、N,N-ジエチルヒドロキシルアミン(DEHA)又はN-n-プロピルヒドロキシルアミンが好ましく、DEHAがより好ましい。
ヒドラジド化合物は、酸のヒドロキシ基をヒドラジノ基(-NH-NH2)で置換してなる化合物、及びその誘導体(ヒドラジノ基に少なくとも1つの置換基が置換されてなる化合物)を意味する。
ヒドラジド化合物は、2つ以上のヒドラジノ基を有していてもよい。
ヒドラジド化合物としては、例えば、カルボン酸ヒドラジド、及びスルホン酸ヒドラジドが挙げられ、カルボヒドラジド(CHZ)が好ましい。
還元性硫黄化合物としては、硫黄原子を含み、還元剤としての機能を有する化合物であれば特に制限されないが、例えば、メルカプトコハク酸、ジチオジグリセロール、ビス(2,3-ジヒドロキシプロピルチオ)エチレン、3-(2,3-ジヒドロキシプロピルチオ)-2-メチル-プロピルスルホン酸ナトリウム、1-チオグリセロール、3-メルカプト-1-プロパンスルホン酸ナトリウム、2-メルカプトエタノール、チオグリコール酸、及び3-メルカプト-1-プロパノールが挙げられる。
なかでも、SH基を有する化合物(メルカプト化合物)が好ましく、1-チオグリセロール、3-メルカプト-1-プロパンスルホン酸ナトリウム、2-メルカプトエタノール、3-メルカプト-1-プロパノール、又はチオグリコール酸がより好ましい。
洗浄液が還元剤を含む場合、還元剤の含有量は特に制限されないが、洗浄液の全質量に対して、0.01~20質量%が好ましく、0.1~5質量%がより好ましい。
また、洗浄液が還元剤を含む場合、還元剤の含有量は、洗浄液中の溶剤を除いた成分の合計質量に対して、0.1~50質量%が好ましく、0.5~30質量%がより好ましい。
なお、これらの還元剤は、市販のものを用いてもよいし、公知の方法に従って合成したものを用いてもよい。
アニオン性界面活性剤は、分子内にアニオン性の親水基と疎水基(親油基)とを有する化合物である。
これらのアニオン性界面活性剤は、洗浄性能を向上させるのみならず、腐食防止性能(特にCo及び/又はCuを含む金属膜に対する腐食防止性能)を向上させる防食剤として機能する。そのため、洗浄液はアニオン性界面活性剤を含むことが好ましい。
リン酸エステル系界面活性剤としては、例えば、リン酸エステル(アルキルエーテルリン酸エステル)、及びポリオキシアルキレンエーテルリン酸エステル、並びにこれらの塩が挙げられる。リン酸エステル及びポリオキシアルキレンエーテルリン酸は、モノエステル及びジエステルの両者を含むことが多いが、モノエステル又はジエステルを単独で使用できる。
リン酸エステル系界面活性剤の塩としては、例えば、ナトリウム塩、カリウム塩、アンモニウム塩、及び有機アミン塩が挙げられる。
リン酸エステル及びポリオキシアルキレンエーテルリン酸エステルが有する1価のアルキル基としては、特に制限されないが、炭素数2~24のアルキル基が好ましく、炭素数6~18のアルキル基がより好ましく、炭素数12~18のアルキル基が更に好ましい。
ポリオキシアルキレンエーテルリン酸エステルが有する2価のアルキレン基としては、特に制限されないが、炭素数2~6のアルキレン基が好ましく、エチレン基、又は1,2-プロパンジイル基がより好ましい。また、ポリオキシアルキレンエーテルリン酸エステルにおけるオキシアルキレン基の繰返し数は、1~12が好ましく、3~10がより好ましい。
ホスホン酸系界面活性剤としては、例えば、アルキルホスホン酸、及びポリビニルホスホン酸や、例えば、特開2012-057108号公報等に記載のアミノメチルホスホン酸等が挙げられる。
スルホン酸系界面活性剤としては、例えば、アルキルスルホン酸、アルキルベンゼンスルホン酸、アルキルナフタレンスルホン酸、アルキルジフェニルエーテルジスルホン酸、アルキルメチルタウリン、スルホコハク酸ジエステル、ポリオキシアルキレンアルキルエーテルスルホン酸、及びこれらの塩が挙げられる。
また、ポリオキシアルキレンアルキルエーテルスルホン酸が有する2価のアルキレン基としては、特に制限されないが、エチレン基、又は1,2-プロパンジイル基が好ましい。また、ポリオキシアルキレンアルキルエーテルスルホン酸におけるオキシアルキレン基の繰返し数は、1~12が好ましく、1~6がより好ましい。
なかでも、炭素数10以上のアルキル基を有するスルホン酸系界面活性剤が好ましく、炭素数12以上のアルキル基を有するスルホン酸系界面活性剤がより好ましく、DBSAが更に好ましい。
カルボン酸系界面活性剤としては、例えば、アルキルカルボン酸、アルキルベンゼンカルボン酸、及びポリオキシアルキレンアルキルエーテルカルボン酸、並びにこれらの塩が挙げられる。
上記のカルボン酸系界面活性剤が有する1価のアルキル基としては、特に制限されないが、炭素数7~25のアルキル基が好ましく、炭素数11~17のアルキル基がより好ましい。
また、ポリオキシアルキレンアルキルエーテルカルボン酸が有する2価のアルキレン基としては、特に制限されないが、エチレン基、又は1,2-プロパンジイル基が好ましい。また、ポリオキシアルキレンアルキルエーテルカルボン酸におけるオキシアルキレン基の繰返し数は、1~12が好ましく、1~6がより好ましい。
硫酸エステル系界面活性剤としては、例えば、硫酸エステル(アルキルエーテル硫酸エステル)、及びポリオキシアルキレンエーテル硫酸エステル、並びにこれらの塩が挙げられる。
硫酸エステル及びポリオキシアルキレンエーテル硫酸エステルが有する1価のアルキル基としては、特に制限されないが、炭素数2~24のアルキル基が好ましく、炭素数6~18のアルキル基がより好ましい。
ポリオキシアルキレンエーテル硫酸エステルが有する2価のアルキレン基としては、特に制限されないが、エチレン基、又は1,2-プロパンジイル基が好ましい。また、ポリオキシアルキレンエーテル硫酸エステルにおけるオキシアルキレン基の繰返し数は、1~12が好ましく、1~6がより好ましい。
硫酸エステル系界面活性剤の具体例としては、ラウリル硫酸エステル、ミリスチル硫酸エステル、及びポリオキシエチレンラウリルエーテル硫酸エステルが挙げられる。
また、洗浄液がアニオン性界面活性剤を含む場合、その含有量は、洗浄液中の溶剤を除いた成分の合計質量に対して、0.05~50質量%が好ましく、0.5~30質量%がより好ましい。
なお、これらのアニオン性界面活性剤としては、市販のものを用いればよい。
洗浄液は、キレート剤を含んでいてもよい。
洗浄液に用いるキレート剤は、半導体基板の洗浄工程において、残渣物に含まれる金属とキレート化する機能を有する化合物である。なかでも、分子内に金属イオンと配位結合する官能基(配位基)を2つ以上有する化合物が好ましい。
なお、本明細書においては、上記の成分A、成分B及び成分Cに含まれる化合物は、キレート剤に含まれないものとする。
洗浄液は、洗浄性能及び腐食防止性能に優れる点で、キレート剤を含むことが好ましい。
有機系キレート剤は、有機化合物からなるキレート剤であり、例えば、ヒドロキシカルボン酸系キレート剤、脂肪族カルボン酸系キレート剤、並びに、少なくとも2つの窒素含有基(窒素原子を含む基)を有し、且つ、カルボキシル基を有さない化合物(以下「特定含窒素キレート剤」とも記載する)が挙げられる。
無機系キレート剤としては、縮合リン酸及びその塩が挙げられる。
キレート剤としては、有機系キレート剤が好ましく、ヒドロキシカルボン酸系キレート剤がより好ましい。
また、ヒドロキシカルボン酸系キレート剤及び脂肪族カルボン酸系キレート剤の炭素数は、15以下が好ましく、12以下がより好ましく、8以下が更に好ましい。下限は特に制限されないが、2以上が好ましい。
ビグアニド化合物が有するビグアニド基の数は特に制限されず、複数のビグアニド基を有していてもよい。
ビグアニド化合物としては、特表2017-504190号公報の段落[0034]~[0055]に記載の化合物が挙げられ、この内容は本明細書に組み込まれる。
ビグアニド基を有する化合物の塩としては、塩酸塩、酢酸塩又はグルコン酸塩が好ましい。
洗浄液がキレート剤を含む場合、洗浄液におけるキレート剤の含有量は、特に制限されないが、腐食防止性能(特にCu及び/又はCoを含む金属膜に対する腐食防止性能)に優れる点で、洗浄液の全質量に対して、0.01質量%以上が好ましく、0.05質量%以上がより好ましい。上限は特に制限されないが、洗浄液の全質量に対して、3質量%以下が好ましく、2質量%以下がより好ましい。
また、洗浄液がキレート剤を含む場合、キレート剤の含有量は、洗浄液中の溶剤を除いた成分の合計質量に対して、0.1~30質量%が好ましく、0.5~20質量%がより好ましい。
洗浄液が成分Dを含む場合、成分Dの含有量は特に制限されないが、洗浄液の全質量に対して、0.01質量%以上が好ましく、0.05質量%以上がより好ましく、0.1質量%以上が更に好ましい。成分Dの含有量の上限値は特に制限されないが、洗浄液の全質量に対して、10.0質量%以下が好ましく、5.0質量%以下がより好ましく、3.0質量%以下が更に好ましい。
また、洗浄液が成分Dを含む場合、成分Dの含有量は、洗浄液中の溶剤を除いた成分の合計質量に対して、0.05質量%以上が好ましく、0.3質量%以上がより好ましく、0.5質量%以上が更に好ましい。上限は特に制限されないが、洗浄液中の溶剤を除いた成分の合計質量に対して、80質量%以下が好ましく、50質量%以下がより好ましく、30質量%以下が更に好ましい。
洗浄液は、第4級アンモニウム化合物を含んでいてもよい。
第4級アンモニウム化合物は、窒素原子に4つの炭化水素基(好ましくはアルキル基)が置換してなる第4級アンモニウムカチオンを有する化合物又はその塩であれば、特に制限されない。第4級アンモニウム化合物としては、例えば、第4級アンモニウム水酸化物、第4級アンモニウムフッ化物、第4級アンモニウム臭化物、第4級アンモニウムヨウ化物、第4級アンモニウムの酢酸塩、及び第4級アンモニウムの炭酸塩が挙げられる。
洗浄液は、腐食防止性能(特にCu及び/又はCoを含む金属膜に対する腐食防止性能)により優れる点で、第4級アンモニウム化合物を含むことが好ましい。
(R8)4N+OH- (2)
式中、R8は、置換基としてヒドロキシ基又はフェニル基を有していてもよいアルキル基を表す。4つのR8は、互いに同一であっても異なっていてもよい。
R8で表されるヒドロキシ基又はフェニル基を有していてもよいアルキル基としては、メチル基、エチル基、プロピル基、ブチル基、2-ヒドロキシエチル基、又はベンジル基が好ましく、メチル基、エチル基、プロピル基、ブチル基、又は2-ヒドロキシエチル基がより好ましく、メチル基、エチル基、又は2-ヒドロキシエチル基が更に好ましい。
上記の具体例以外の第4級アンモニウム化合物としては、例えば、特開2018-107353号公報の段落[0021]に記載の化合物が援用でき、この内容は本明細書に組み込まれる。
非対称構造を有する第4級アンモニウム化合物としては、例えば、TMEAH、DEDMAH、MTEAH、コリン、及びビス(2-ヒドロキシエチル)ジメチルアンモニウムヒドロキシドが挙げられ、MTEAHが好ましい。
洗浄液が第4級アンモニウム化合物を含む場合、その含有量は、洗浄性能により優れる点で、洗浄液の全質量に対して、0.05質量%以上が好ましく、0.1質量%以上がより好ましく、0.2質量%以上が更に好ましい。第4級アンモニウム化合物の含有量の上限は特に制限されないが、洗浄工程における残渣物粒子の凝集及び/又は残渣物の再吸着による洗浄性能の低下を抑制する点で、10質量%以下が好ましく、5質量%以下がより好ましく、3質量%以下が更に好ましい。
また、洗浄液が第4級アンモニウム化合物を含む場合、その含有量は、洗浄液中の溶剤を除いた成分の合計質量に対して、0.2~30質量%が好ましく、0.5~15質量%がより好ましい。
洗浄液は、アニオン性界面活性剤以外の他の界面活性剤を含んでいてもよい。
他の界面活性剤としては、分子内に親水基と疎水基(親油基)とを有するアニオン性界面活性剤以外の化合物であれば特に制限されず、例えば、カチオン性界面活性剤、ノニオン性界面活性剤、及び両性界面活性剤が挙げられる。
カチオン性界面活性剤としては、例えば、第1級~第3級のアルキルアミン塩(例えば、モノステアリルアンモニウムクロライド、ジステアリルアンモニウムクロライド、及びトリステアリルアンモニウムクロライド等)、並びに変性脂肪族ポリアミン(例えば、ポリエチレンポリアミン等)が挙げられる。
ノニオン性界面活性剤としては、例えば、ポリオキシアルキレンアルキルエーテル(例えば、ポリオキシエチレンステアリルエーテル等)、ポリオキシアルキレンアルケニルエーテル(例えば、ポリオキシエチレンオレイルエーテル等)、ポリオキシエチレンアルキルフェニルエーテル(例えば、ポリオキシエチレンノニルフェニルエーテル等)、ポリオキシアルキレングリコール(例えば、ポリオキシプロピレンポリオキシエチレングリコール等)、ポリオキシアルキレンモノアルキレート(モノアルキル脂肪酸エステルポリオキシアルキレン)(例えば、ポリオキシエチレンモノステアレート、及びポリオキシエチレンモノオレート等のポリオキシエチレンモノアルキレート)、ポリオキシアルキレンジアルキレート(ジアルキル脂肪酸エステルポリオキシアルキレン)(例えば、ポリオキシエチレンジステアレート、及びポリオキシエチレンジオレート等のポリオキシエチレンジアルキレート)、ビスポリオキシアルキレンアルキルアミド(例えば、ビスポリオキシエチレンステアリルアミド等)、ソルビタン脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステル、ポリオキシエチレンアルキルアミン、グリセリン脂肪酸エステル、オキシエチレンオキシプロピレンブロックコポリマー、アセチレングリコール系界面活性剤、及びアセチレン系ポリオキシエチレンオキシドが挙げられる。
両性界面活性剤としては、例えば、カルボキシベタイン(例えば、アルキル-N,N-ジメチルアミノ酢酸ベタイン及びアルキル-N,N-ジヒドロキシエチルアミノ酢酸ベタイン等)、スルホベタイン(例えば、アルキル-N,N-ジメチルスルホエチレンアンモニウムベタイン等)、並びに、イミダゾリニウムベタイン(例えば、2-アルキル-N-カルボキシメチル-N-ヒドロキシエチルイミダソリニウムベタイン等)が挙げられる。
洗浄液は、必要に応じて、上記成分以外の添加剤を含んでいてもよい。そのような添加剤としては、pH調整剤、防食剤(成分Dに含まれる成分を除く)、重合体、フッ素化合物、及び有機溶剤が挙げられる。
洗浄液は、洗浄液のpHを調整及び維持するためにpH調整剤を含んでいてもよい。pH調整剤としては、上記成分以外の塩基性化合物及び酸性化合物が挙げられる。
塩基性有機化合物は、上記成分とは異なる塩基性の有機化合物である。塩基性有機化合物としては、例えば、アミンオキシド、ニトロ、ニトロソ、オキシム、ケトオキシム、アルドオキシム、ラクタム、イソシアニド化合物、及び尿素が挙げられる。
塩基性無機化合物としては、例えば、アルカリ金属水酸化物、アルカリ土類金属水酸化物、及びアンモニアが挙げられる。
アルカリ金属水酸化物としては、例えば、水酸化リチウム、水酸化ナトリウム、水酸化カリウム、及び水酸化セシウムが挙げられる。アルカリ土類金属水酸化物としては、例えば、水酸化カルシウム、水酸化ストロンチウム、及び水酸化バリウムが挙げられる。
これらの塩基性化合物は、市販のものを用いてもよいし、公知の方法によって適宜合成したものを用いてもよい。
無機酸としては、例えば、塩酸、硫酸、亜硫酸、硝酸、亜硝酸、リン酸、ホウ酸、及び六フッ化リン酸が挙げられる。また、無機酸の塩を使用してもよく、例えば、無機酸のアンモニウム塩が挙げられ、より具体的には、塩化アンモニウム、硫酸アンモニウム、亜硫酸アンモニウム、硝酸アンモニウム、亜硝酸アンモニウム、リン酸アンモニウム、ホウ酸アンモニウム、及び六フッ化リン酸アンモニウムが挙げられる。
無機酸としては、リン酸、又はリン酸塩が好ましく、リン酸がより好ましい。
また、洗浄液に含まれるキレート剤、及び/又はアニオン性界面活性剤が、洗浄液のpHを低下させるための酸性化合物としての役割を兼ねていてもよい。
酸性化合物は、市販のものを用いてもよいし、公知の方法によって適宜合成したものを用いてもよい。
洗浄液がpH調整剤を含む場合、その含有量は、他の成分の種類及び量、並びに目的とする洗浄液のpHに応じて選択されるが、洗浄液の全質量に対して、0.01~3質量%が好ましく、0.05~1質量%がより好ましい。
また、洗浄液がpH調整剤を含む場合、その含有量は、他の成分の種類及び量、並びに目的とする洗浄液のpHに応じて選択されるが、洗浄液中の溶剤を除いた成分の合計質量に対して、0.05~10質量%が好ましく、0.2~5質量%がより好ましい。
他の防食剤としては、例えば、フルクトース、グルコース及びリボース等の糖類、エチレングリコール、プロピレングリコール、及びグリセリン等のポリオール化合物、ポリアクリル酸、ポリマレイン酸、及びこれらの共重合体等のポリカルボン酸化合物、ポリビニルピロリドン、シアヌル酸、バルビツール酸及びその誘導体、グルクロン酸、スクアリン酸、α-ケト酸、アデノシン及びその誘導体、プリン化合物及びその誘導体、フェナントロリン、レゾルシノール、ヒドロキノン、ニコチンアミド及びその誘導体、フラボノ-ル及びその誘導体、アントシアニン及びその誘導体、並びにこれらの組み合わせが挙げられる。
フッ素化合物としては、特開2005-150236号公報の段落[0013]~[0015]に記載の化合物が挙げられ、この内容は本明細書に組み込まれる。
有機溶剤としては、公知の有機溶剤をいずれも使用できるが、アルコール、及びケトン等の親水性有機溶剤が好ましい。有機溶剤は、単独で用いてもよく、2種類以上を組み合わせて用いてもよい。
重合体、フッ素化合物、及び有機溶剤の使用量は特に制限されず、本発明の効果を妨げない範囲で適宜設定すればよい。
<pH>
洗浄液は、アルカリ性を示すことが好ましい。即ち、洗浄液のpHは、25℃において、7.0超であることが好ましい。
洗浄液のpHは、25℃において、8.0以上がより好ましく、洗浄性能並びに腐食防止性能(特にCo及び/又はCuを含む金属膜に対する腐食防止性能)により優れる点で、8.5超が更に好ましく、9.0以上が特に好ましい。洗浄液のpHの上限は特に制限されないが、25℃において、12.0以下が好ましく、腐食防止性能(特にW及び/又はCuを含む金属膜に対する腐食防止性能)により優れる点で、11.5未満がより好ましく、11.0以下が更に好ましい。
洗浄液のpHは、上記のpH調整剤、並びに、上記の成分A、成分B、成分C、成分D、第4級アンモニウム化合物等のpH調整剤の機能を有する成分を使用することにより、調整すればよい。
なお、洗浄液のpHは、公知のpHメーターを用いて、JIS Z8802-1984に準拠した方法により測定できる。
洗浄液は、液中に不純物として含まれる金属(Fe、Co、Na、K、Cu、Mg、Mn、Li、Al、Cr、Ni、Zn、Sn及びAgの金属元素)の含有量(イオン濃度として測定される)がいずれも5質量ppm以下であることが好ましく、1質量ppm以下であることがより好ましい。最先端の半導体素子の製造においては、更に高純度の洗浄液が求められることが想定されることから、その金属含有量が1質量ppmよりも低い値、すなわち、質量ppbオーダー以下であることが更に好ましく、100質量ppb以下であることが特に好ましく、10質量ppb未満であることが最も好ましい。下限は特に制限されないが、0が好ましい。
他の金属含有量の低減方法としては、原材料又は製造された洗浄液を収容する容器として、後述する不純物の溶出が少ない容器を用いることが挙げられる。また、洗浄液の製造時に配管等の部材から金属成分が溶出しないように、配管内壁等の部材の接液部にフッ素系樹脂のライニングを施すことも挙げられる。
洗浄液は、粗大粒子を含んでいてもよいが、その含有量が低いことが好ましい。ここで、粗大粒子とは、粒子の形状を球体とみなした場合における直径(粒径)が0.4μm以上である粒子を意味する。
洗浄液における粗大粒子の含有量としては、粒径0.4μm以上の粒子の含有量が、洗浄液1mLあたり1000個以下であることが好ましく、500個以下であることがより好ましい。下限は特に制限されないが、0が挙げられる。また、上記の測定方法で測定された粒径0.4μm以上の粒子の含有量が検出限界以下であることが更に好ましい。
洗浄液に含まれる粗大粒子は、原料に不純物として含まれる塵、埃、有機固形物、及び無機固形物等の粒子、並びに洗浄液の調製中に汚染物として持ち込まれる塵、埃、有機固形物、及び無機固形物等の粒子であって、最終的に洗浄液中で溶解せずに粒子として存在するものが該当する。
洗浄液中に存在する粗大粒子の含有量は、レーザを光源とした光散乱式液中粒子測定方式における市販の測定装置を利用して液相で測定できる。
粗大粒子の除去方法としては、例えば、後述するフィルタリング等の精製処理が挙げられる。
洗浄液をキットとする方法としては、例えば、第1液として成分A及び成分Bを含む液組成物を調製し、第2液として成分C及び他の成分を含む液組成物を調製する態様が挙げられる。
洗浄液は、公知の方法により製造できる。以下、洗浄液の製造方法について詳述する。
洗浄液の調液方法は特に制限されず、例えば、上述した各成分を混合することにより洗浄液を製造できる。上述した各成分を混合する順序、及び/又はタイミングは特に制限されず、例えば、精製した純水を入れた容器に、成分A、成分B及び成分C、並びに、任意成分として成分D及び第4級アンモニウム化合物を順次添加した後、撹拌して混合するとともに、pH調整剤を添加して混合液のpHを調整することにより、調製する方法が挙げられる。また、水及び各成分を容器に添加する場合、一括して添加してもよいし、複数回にわたって分割して添加してもよい。
洗浄液を調製するための原料のいずれか1種以上に対して、事前に精製処理を行うことが好ましい。精製処理としては、特に制限されず、蒸留、イオン交換、及びろ過等の公知の方法が挙げられる。
精製の程度としては、特に制限されないが、原料の純度が99質量%以上となるまで精製することが好ましく、原料の純度が99.9質量%以上となるまで精製することがより好ましい。
精製処理として、上述した精製方法を複数組み合わせて実施してもよい。例えば、原料に対して、RO膜に通液する1次精製を行った後、カチオン交換樹脂、アニオン交換樹脂、又は混床型イオン交換樹脂からなる精製装置に通液する2次精製を実施してもよい。 また、精製処理は、複数回実施してもよい。
フィルタリングに用いるフィルタとしては、従来からろ過用途に用いられているものであれば特に制限されない。例えば、ポリテトラフルオロエチレン(PTFE)、及びテトラフルオロエチレンパーフルオロアルキルビニルエーテル共重合体(PFA)等のフッ素樹脂、ナイロン等のポリアミド系樹脂、並びにポリエチレン及びポリプロピレン(PP)等のポリオレフィン樹脂(高密度又は超高分子量を含む)からなるフィルタが挙げられる。これらの材料のなかでもポリエチレン、ポリプロピレン(高密度ポリプロピレンを含む)、フッ素樹脂(PTFE及びPFAを含む)、及びポリアミド系樹脂(ナイロンを含む)からなる群より選ばれる材料が好ましく、フッ素樹脂のフィルタがより好ましい。これらの材料により形成されたフィルタを使用して原料のろ過を行うことで、欠陥の原因となり易い極性の高い異物を効果的に除去できる。
洗浄液(キット又は後述する希釈液の態様を含む)は、腐食性等の問題が生じない限り、任意の容器に充填して保管、運搬、及び使用できる。
また、洗浄液を収容する容器としては、その収容部の内壁等の各液との接液部が、フッ素系樹脂(パーフルオロ樹脂)、又は防錆及び金属溶出防止処理が施された金属で形成された容器が好ましい。
容器の内壁は、ポリエチレン樹脂、ポリプロピレン樹脂、及びポリエチレン-ポリプロピレン樹脂からなる群より選択される1種以上の樹脂、もしくは、これとは異なる樹脂、又は、ステンレス、ハステロイ、インコネル、及びモネル等、防錆及び金属溶出防止処理が施された金属から形成されることが好ましい。
このような内壁がフッ素系樹脂である容器の具体例としては、例えば、Entegris社製 FluoroPurePFA複合ドラムが挙げられる。また、特表平3-502677号公報の第4頁、国際公開第2004/016526号明細書の第3頁、並びに国際公開第99/046309号明細書の第9頁及び16頁に記載の容器も使用できる。
上記電解研磨された金属材料の製造に用いられる金属材料は、クロム及びニッケルからなる群より選択される少なくとも1種を含み、クロム及びニッケルの含有量の合計が金属材料全質量に対して25質量%超である金属材料であることが好ましい。そのような金属材料としては、例えば、ステンレス鋼、及びニッケル-クロム合金が挙げられる。
金属材料におけるクロム及びニッケルの含有量の合計は、金属材料全質量に対して30質量%以上がより好ましい。
なお、金属材料におけるクロム及びニッケルの含有量の合計の上限値としては特に制限されないが、90質量%以下が好ましい。
洗浄液の製造、容器の開封及び洗浄、洗浄液の充填を含めた取り扱い、処理分析、並びに測定は、全てクリーンルームで行うことが好ましい。クリーンルームは、14644-1クリーンルーム基準を満たすことが好ましい。ISO(国際標準化機構)クラス1、ISOクラス2、ISOクラス3、及びISOクラス4のいずれかを満たすことが好ましく、ISOクラス1又はISOクラス2を満たすことがより好ましく、ISOクラス1を満たすことが更に好ましい。
上述した洗浄液は、水等の希釈剤を用いて希釈する希釈工程を経た後、半導体基板の洗浄に供されることが好ましい。
また、欠陥抑制性能により優れる点で、洗浄液は水で希釈されることが好ましい。
また、希釈洗浄液のpHは、25℃において、7.0超が好ましく、7.5以上がより好ましく、8.0以上が更に好ましい。希釈洗浄液のpHの上限は、25℃において、13.0以下が好ましく、12.5以下がより好ましく、12.0以下が更に好ましい。
希釈洗浄液における成分Bの含有量は、特に制限されないが、Cuを含む金属膜に対する洗浄性能により優れる点で、希釈洗浄液の全質量に対して、0.00005質量%以上が好ましく、0.00008質量%以上がより好ましく、0.0001質量%以上が更に好ましい。上限は特に制限されないが、腐食防止性能(特にCuを含む金属膜に対する腐食防止性能)により優れる点で、希釈洗浄液の全質量に対して0.02質量%以下が好ましく、0.015質量%以下がより好ましく、0.012質量%以下が更に好ましい。
希釈洗浄液における成分Cの含有量は、特に制限されないが、希釈洗浄液の全質量に対して、0.0003~0.3質量%が好ましく、0.0005~0.15質量%がより好ましく、0.005~0.12質量%が更に好ましい。
希釈洗浄液における水の含有量は、成分A、成分B、成分C、及び、上記任意成分の残部であればよい。水の含有量は、例えば、希釈洗浄液の全質量に対して、90質量%以上が好ましく、99.3質量%以上がより好ましく、99.6質量%以上が更に好ましく、99.85質量%以上が特に好ましい。上限値は特に制限されないが、希釈洗浄液の全質量に対して、99.99質量%以下が好ましく、99.95質量%以下がより好ましい。
希釈洗浄液が含窒素へテロ芳香族化合物を含む場合、希釈洗浄液における含窒素へテロ芳香族化合物の含有量は、特に制限されないが、希釈洗浄液の全質量に対して、0.0001~0.1質量%が好ましく、0.0005~0.05質量%がより好ましい。
希釈洗浄液が還元剤を含む場合、還元剤の含有量は特に制限されないが、希釈洗浄液の全質量に対して、0.0001~0.2質量%が好ましく、0.001~0.05質量%がより好ましい。
希釈洗浄液がアニオン性界面活性剤を含む場合、その含有量は、希釈洗浄液の全質量に対して、0.0001~0.05質量%が好ましく、0.0005~0.02質量%がより好ましい。
希釈洗浄液におけるキレート剤の含有量は、特に制限されないが、腐食防止性能(特にCu及び/又はCoを含む金属膜に対する腐食防止性能)に優れる点で、希釈洗浄液の全質量に対して、0.0001質量%以上が好ましく、0.0005質量%以上がより好ましい。上限は特に制限されないが、希釈洗浄液の全質量に対して、0.03質量%以下が好ましく、0.02質量%以下がより好ましい。
希釈洗浄液が第4級アンモニウム化合物を含む場合、その含有量は、洗浄性能により優れる点で、希釈洗浄液の全質量に対して、0.0005質量%以上が好ましく、0.001質量%以上がより好ましく、0.002質量%以上が更に好ましい。第4級アンモニウム化合物の含有量の上限は特に制限されないが、洗浄工程における残渣物粒子の凝集及び/又は残渣物の再吸着による洗浄性能の低下を抑制する点で、0.1質量%以下が好ましく、0.05質量%以下がより好ましく、0.03質量%以下が更に好ましい。
希釈洗浄液がpH調整剤を含む場合、その含有量は、他の成分の種類及び量、並びに目的とする希釈洗浄液のpHに応じて選択されるが、希釈洗浄液の全質量に対して、0.0001~0.03質量%が好ましく、0.0005~0.01質量%がより好ましい。
精製処理としては、特に制限されず、上述した洗浄液に対する精製処理として記載した、イオン交換樹脂又はRO膜を用いたイオン成分低減処理、及びフィルタリングを用いた異物除去が挙げられ、これらのうちいずれかの処理を行うことが好ましい。
洗浄液は、化学機械研磨(CMP)処理が施された半導体基板を洗浄する洗浄工程に使用される。また、洗浄液は、半導体基板の製造プロセスにおける半導体基板の洗浄に使用でき、後述するバフ研磨処理用組成物としても使用できる。
上述のとおり、半導体基板の洗浄には、洗浄液を希釈して得られる希釈洗浄液を使用してもよい。
洗浄液の洗浄対象物としては、例えば、金属含有物を有する半導体基板が挙げられる。
なお、本明細書における「半導体基板上」とは、例えば、半導体基板の表裏、側面、及び、溝内のいずれも含む。また、半導体基板上の金属含有物とは、半導体基板の表面上に直接金属含有物がある場合のみならず、半導体基板上に他の層を介して金属含有物がある場合も含む。
また、金属含有物は、これらの化合物のうちの2種以上を含む混合物でもよい。
なお、上記酸化物、窒化物、及び、酸窒化物は、金属を含む、複合酸化物、複合窒化物、及び、複合酸窒化物でもよい。
金属含有物中の金属原子の含有量は、金属含有物の全質量に対して、10質量%以上が好ましく、30質量%以上がより好ましく、50質量%以上が更に好ましい。上限は、金属含有物が金属そのものであってもよいことから、100質量%である。
シリコンウエハとしては、シリコンウエハに5価の原子(例えば、リン(P)、ヒ素(As)、及びアンチモン(Sb)等)をドープしたn型シリコンウエハ、並びにシリコンウエハに3価の原子(例えば、ホウ素(B)、及びガリウム(Ga)等)をドープしたp型シリコンウエハであってもよい。シリコンウエハのシリコンとしては、例えば、アモルファスシリコン、単結晶シリコン、多結晶シリコン、及びポリシリコンのいずれであってもよい。
なかでも、洗浄液は、シリコンウエハ、シリコンカーバイドウエハ、及びシリコンを含む樹脂系ウエハ(ガラスエポキシウエハ)等のシリコン系材料からなるウエハに有用である。
絶縁膜の具体例としては、シリコン酸化膜(例えば、二酸化ケイ素(SiO2)膜、及びオルトケイ酸テトラエチル(Si(OC2H5)4)膜(TEOS膜)等)、シリコン窒化膜(例えば、窒化シリコン(Si3N4)、及び窒化炭化シリコン(SiNC)等)、並びに、低誘電率(Low-k)膜(例えば、炭素ドープ酸化ケイ素(SiOC)膜、及びシリコンカーバイド(SiC)膜等)が挙げられる。
半導体基板は、銅及びコバルトからなる群より選択される少なくとも1種を含む金属膜を有することが好ましい。また、半導体基板は、タングステンを含む金属膜を有することも好ましい。
銅合金配線膜の具体例としては、アルミニウム(Al)、チタン(Ti)、クロム(Cr)、マンガン(Mn)、タンタル(Ta)、及びタングステン(W)から選ばれる1種以上の金属と銅とからなる合金製の配線膜が挙げられる。より具体的には、銅-アルミニウム合金配線膜(CuAl合金配線膜)、銅-チタン合金配線膜(CuTi合金配線膜)、銅-クロム合金配線膜(CuCr合金配線膜)、銅-マンガン合金配線膜(CuMn合金配線膜)、銅-タンタル合金配線膜(CuTa合金配線膜)、及び銅-タングステン合金配線膜(CuW合金配線膜)が挙げられる。
コバルト合金金属膜の具体例としては、チタン(Ti)、クロム(Cr)、鉄(Fe)、ニッケル(Ni)、モリブデン(Mo)、パラジウム(Pd)、タンタル(Ta)、及びタングステン(W)から選ばれる1種以上の金属とコバルトとからなる合金製の金属膜が挙げられる。より具体的には、コバルト-チタン合金金属膜(CoTi合金金属膜)、コバルト-クロム合金金属膜(CoCr合金金属膜)、コバルト-鉄合金金属膜(CoFe合金金属膜)、コバルト-ニッケル合金金属膜(CoNi合金金属膜)、コバルト-モリブデン合金金属膜(CoMo合金金属膜)、コバルト-パラジウム合金金属膜(CoPd合金金属膜)、コバルト-タンタル合金金属膜(CoTa合金金属膜)、及びコバルト-タングステン合金金属膜(CoW合金金属膜)が挙げられる。
洗浄液は、コバルト含有膜を有する基板に有用である。コバルト含有膜のうち、コバルト金属膜は配線膜として使用されることが多く、コバルト合金金属膜はバリアメタルとして使用されることが多い。
タングステン合金金属膜の具体例としては、例えば、タングステン-チタン合金金属膜(WTi合金金属膜)、及びタングステン-コバルト合金金属膜(WCo合金金属膜)が挙げられる。
タングステン含有膜は、バリアメタルとして使用されることが多い。
絶縁膜の形成方法としては、例えば、半導体基板を構成するウエハに対して、酸素ガス存在下で熱処理を行うことによりシリコン酸化膜を形成し、次いで、シラン及びアンモニアのガスを流入して、化学気相蒸着(CVD:Chemical Vapor Deposition)法によりシリコン窒化膜を形成する方法が挙げられる。
銅含有配線膜、コバルト含有膜、及びタングステン含有膜の形成方法としては、例えば、上記の絶縁膜を有するウエハ上に、レジスト等の公知の方法で回路を形成し、次いで、めっき及びCVD法等の方法により、銅含有配線膜、コバルト含有膜、及びタングステン含有膜を形成する方法が挙げられる。
CMP処理は、例えば、金属配線膜、バリアメタル、及び絶縁膜を有する基板の表面を、研磨微粒子(砥粒)を含む研磨スラリーを用いる化学作用と機械的研磨の複合作用で平坦化する処理である。
CMP処理が施された半導体基板の表面には、CMP処理で使用した砥粒(例えば、シリカ及びアルミナ等)、研磨された金属配線膜、及びバリアメタルに由来する金属不純物(金属残渣)等の不純物が残存することがある。これらの不純物は、例えば、配線間を短絡させ、半導体基板の電気的特性を劣化させるおそれがあるため、CMP処理が施された半導体基板は、これらの不純物を表面から除去するための洗浄処理に供される。
CMP処理が施された半導体基板の具体例としては、精密工学会誌 Vol.84、No.3、2018に記載のCMP処理が施された基板が挙げられるが、これに制限されるものではない。
洗浄液の洗浄対象物である半導体基板の表面は、CMP処理が施された後、バフ研磨処理が施されていてもよい。
バフ研磨処理は、研磨パッドを用いて半導体基板の表面における不純物を低減する処理である。具体的には、CMP処理が施された半導体基板の表面と研磨パッドとを接触させて、その接触部分にバフ研磨用組成物を供給しながら半導体基板と研磨パッドとを相対摺動させる。その結果、半導体基板の表面の不純物が、研磨パッドによる摩擦力及びバフ研磨用組成物による化学的作用によって除去される。
また、バフ研磨処理の一実施形態としては、バフ研磨用組成物として、上記の洗浄液を用いて半導体基板にバフ研磨処理を施すことが好ましい。
バフ研磨処理において使用する研磨装置及び研磨条件については、半導体基板の種類及び除去対象物に応じて、公知の装置及び条件から適宜選択できる。バフ研磨処理としては、例えば、国際公開2017/169539号の段落[0085]~[0088]に記載の処理が挙げられ、この内容は本明細書に組み込まれる。
半導体基板の洗浄方法は、上記の洗浄液を用いて、CMP処理が施された半導体基板を洗浄する洗浄工程を含むものであれば特に制限されない。半導体基板の洗浄方法は、上記の希釈工程で得られる希釈洗浄液をCMP処理が施された半導体基板に適用して洗浄する工程を含むことが、好ましい。
上記洗浄工程は、1回のみ実施してもよく、2回以上実施してもよい。2回以上洗浄する場合には同じ方法を繰り返してもよいし、異なる方法を組み合わせてもよい。
機械的撹拌方法としては、例えば、半導体基板上で洗浄液を循環させる方法、半導体基板上で洗浄液を流過又は噴霧させる方法、及び超音波又はメガソニックにて洗浄液を撹拌する方法が挙げられる。
リンス工程は、半導体基板の洗浄工程の後に連続して行われ、リンス溶剤(リンス液)を用いて5秒間~5分間にわたってすすぐ工程であることが好ましい。リンス工程は、上述の機械的撹拌方法を用いて行ってもよい。
リンス溶剤を半導体基板に接触させる方法としては、上述した洗浄液を半導体基板に接触させる方法を同様に適用できる。
乾燥方法としては、特に制限されず、例えば、スピン乾燥法、半導体基板上に乾性ガスを流過させる方法、ホットプレートもしくは赤外線ランプのような加熱手段によって基板を加熱する方法、マランゴニ乾燥法、ロタゴニ乾燥法、IPA(イソプロピルアルコール)乾燥法、及びそれらの任意の組み合わせが挙げられる。
また、実施例及び比較例の洗浄液の製造にあたって、容器の取り扱い、洗浄液の調液、充填、保管及び分析測定は、全てISOクラス2以下を満たすレベルのクリーンルームで行った。測定精度向上のため、洗浄液の金属含有量の測定において、通常の測定で検出限界以下のものの測定を行う際には、洗浄液を体積換算で100分の1に濃縮して測定を行い、濃縮前の溶液の濃度に換算して含有量の算出を行った。
洗浄液を製造するために、以下の化合物を使用した。なお、実施例で使用した各種成分はいずれも、半導体グレードに分類されるもの、又は、それに準ずる高純度グレードに分類されるものを使用した。
・ グリシン:富士フイルム和光純薬(株)製
・ ヒスチジン:富士フイルム和光純薬(株)製
・ システイン:富士フイルム和光純薬(株)製
・ アルギニン:富士フイルム和光純薬(株)製
・ メチオニン:富士フイルム和光純薬(株)製
・ サルコシン:富士フイルム和光純薬(株)製
・ β-アラニン:富士フイルム和光純薬(株)製
・ ジエチレントリアミン五酢酸(DTPA):富士フイルム和光純薬(株)製(アミノポリカルボン酸に該当する)
・ エチレンジアミン四酢酸(EDTA):キレスト社製(アミノポリカルボン酸に該当する)
・ トランス-1,2-ジアミノシクロヘキサン四酢酸(CyDTA):富士フイルム和光純薬(株)製(アミノポリカルボン酸に該当する)
・ ニトリロトリス(メチレンホスホン酸)(NTPO):富士フイルム和光純薬(株)製(ポリホスホン酸に該当する)
・ N,N,N’,N’-エチレンジアミンテトラキス(メチレンホスホン酸)(EDTPO):サーモフォス社製「Dequest 2066」(ポリホスホン酸に該当する)
・ 2-アミノ-2-メチル-1-プロパノール(AMP):富士フイルム和光純薬(株)製(アミノアルコールに該当する。)
・ 2-アミノピリミジン:富士フイルム和光純薬(株)製(防食剤(含窒素へテロ芳香族化合物)に該当する)
・ アデニン:富士フイルム和光純薬(株)製(防食剤(含窒素へテロ芳香族化合物)に該当する)
・ ピラゾール:富士フイルム和光純薬(株)製(防食剤(含窒素へテロ芳香族化合物)に該当する)
・ 3-アミノ-5-メチルピラゾール:東京化成(株)製(防食剤(含窒素へテロ芳香族化合物)に該当する)
・ 2-アミノベンゾイミダゾール:富士フイルム和光純薬(株)製(防食剤(含窒素へテロ芳香族化合物)に該当する)
・ クロルヘキシジングルコン酸塩(CHG):富士フイルム和光純薬(株)製(キレート剤に該当する)
・ グルコン酸:富士フイルム和光純薬(株)製(キレート剤に該当する)
・ クエン酸:扶桑化学工業(株)製(キレート剤に該当する)
・ アスコルビン酸:富士フイルム和光純薬(株)製(防食剤(還元剤)に該当する)
・ ジエチルヒドロキシルアミン(DEHA):富士フイルム和光純薬(株)製(防食剤(還元剤)に該当する)
・ ラウリルリン酸エステル:日光ケミカルズ(株)製「ホステンHLP」(防食剤(アニオン性界面活性剤)に該当する)
・ ドデシルベンゼンスルホン酸(DBSA):富士フイルム和光純薬(株)製(防食剤(アニオン性界面活性剤)に該当する)
・ メチルトリエチルアンモニウムヒドロキシド(MTEAH):富士フイルム和光純薬(株)製
・ テトラエチルアンモニウムヒドロキシド(TEAH):富士フイルム和光純薬(株)製
次に、洗浄液の製造方法について、実施例1を例に説明する。
超純水に、グリシン、DTPA(ジエチレントリアミン五酢酸)、AMP(2-アミノ-2-メチル-1-プロパノール)、2-アミノピリミジン、及び、ホステンHLPを、後述の表1及び表2に記載の含有量となる量でそれぞれ添加した後、調製される洗浄液のpHが10.5となるようにpH調整剤を添加した。得られた混合液を撹拌機を用いて十分に攪拌することにより、実施例1の洗浄液を得た。
「比率1」欄の数値は、成分Aの含有量(複数使用した場合は合計含有量である。以下同じ。)に対する成分Bの含有量(成分Bの含有量/成分Aの含有量)の質量比を示す。
「比率2」欄の数値は、成分Aの含有量と成分Bの含有量との和に対する成分Cの含有量(成分Cの含有量/(成分Aの含有量+成分Bの含有量))の質量比を示す。
「比率3」欄の数値は、成分Aの含有量と成分Bの含有量との和に対する成分Dの含有量(成分Dの含有量/(成分Aの含有量+成分Bの含有量))の質量比を示す。
「pH」欄の数値は、上記のpHメーターにより測定した洗浄液の25℃におけるpHを示す。
各実施例及び各比較例で製造された洗浄液につき、金属含有量を測定した。
金属含有量の測定は、Agilent 8800 トリプル四重極ICP-MS(半導体分析用、オプション#200)を用いて、以下の測定条件で行った。
サンプル導入系としては石英のトーチ、同軸型PFAネブライザ(自吸用)及び白金インターフェースコーンを使用した。クールプラズマ条件の測定パラメータは以下のとおりである。
・ RF(Radio Frequency)出力(W):600
・ キャリアガス流量(L/分):0.7
・ メークアップガス流量(L/分):1
・ サンプリング深さ(mm):18
金属含有量の測定結果を、表1及び表2の「金属含有量(ppb)」欄に示す(単位:質量ppb)。表1及び表2における「<10」は、洗浄液における金属含有量が洗浄液の全質量に対して10質量ppb未満であったことを表す。
上記の方法で製造した洗浄液を用いて、化学機械研磨を施した金属膜を洗浄した際の洗浄性能(残渣物除去性能)を評価した。
各実施例及び各比較例の洗浄液1mLを分取し、超純水により体積比で100倍に希釈して、希釈洗浄液のサンプルを調製した。
表面に銅、タングステン又はコバルトからなる金属膜を有するウエハ(直径8インチ)を、FREX300S-II(研磨装置、(株)荏原製作所製)を用いて研磨した。表面に銅からなる金属膜を有するウエハに対しては、研磨液としてCSL9044C及びBSL8176C(商品名、いずれも富士フイルムプラナーソリューションズ社製)をそれぞれ使用して研磨を行った。これにより、研磨液による洗浄性能評価のばらつきを抑えた。同様に、表面にコバルトからなる金属膜を有するウエハに対しては、研磨液としてCSL5340C及びCSL5250C(商品名、いずれも富士フイルムプラナーソリューションズ社製)をそれぞれ使用して研磨を行った。表面にタングステンからなる金属膜を有するウエハに対しては、W-2000(商品名、キャボット社製)のみを使用して研磨を行った。研磨圧力は2.0psiであり、研磨液の供給速度は0.28mL/(分・cm2)であった。研磨時間は60秒間であった。
その後、室温(23℃)に調整した各希釈洗浄液のサンプルを用いて、研磨されたウエハを30秒間かけて洗浄し、次いで、乾燥処理した。
「A」:ウエハあたりの欠陥数が200個未満
「B」:ウエハあたりの欠陥数が200個以上300個未満
「C」:ウエハあたりの欠陥数が300個以上500個未満
「D」:ウエハあたりの欠陥数が500個以上
各実施例及び各比較例の洗浄液0.02mLを分取し、超純水により体積比で100倍に希釈して、希釈洗浄液のサンプルを調製した。
表面に銅、タングステン又はコバルトからなる金属膜を有するウエハ(直径12インチ)をカットし、2cm□のウエハクーポンをそれぞれ準備した。各金属膜の厚さは200nmとした。上記の方法で製造した希釈洗浄液のサンプル(温度:23℃)中にウエハクーポンを浸漬し、攪拌回転数250rpmにて、3分間の浸漬処理を行った。各金属膜について、浸漬処理前後で、各希釈洗浄液中の銅、タングステン又はコバルトの含有量を測定した。得られた測定結果から単位時間当たりの腐食速度(単位:Å/分)を算出した。下記の評価基準により洗浄液の腐食防止性能を評価した。それらの結果を表1及び表2に示す。
なお、腐食速度が低いほど、洗浄液の腐食防止性能が優れる。
「B」:腐食速度が0.5Å/分以上、1.0Å/分未満
「C」:腐食速度が1.0Å/分以上、3.0Å/分未満
「D」:腐食速度が3.0Å/分以上
成分Aの含有量が洗浄液の全質量に対して0.003質量%以上である場合、Coを含む金属膜に対する洗浄性能により優れることが確認された(実施例22と実施例23との比較)。
成分Aの含有量が洗浄液の全質量に対して1.0質量%以下である場合、Coを含む金属膜に対する腐食防止性能により優れることが確認された(実施例25と実施例26との比較)。
成分Bの含有量が洗浄液の全質量に対して0.005質量%以上である場合、Cuを含む金属膜に対する洗浄性能により優れることが確認された(実施例22と実施例23との比較)。
成分Bの含有量が洗浄液の全質量に対して1.5質量%以下である場合、Cuを含む金属膜に対する腐食防止性能により優れることが確認された(実施例25と実施例26との比較)。
洗浄液が、成分Dとして還元剤を含む場合、Cuを含む金属膜に対する腐食防止性能により優れることが確認された(実施例36と実施例42との比較)。
洗浄液が、成分Dとして2種以上の還元剤を含む場合、Wを含む金属膜に対する腐食防止性能により優れることが確認された(実施例42と実施例43との比較)。
洗浄液が、2種以上の第4級アンモニウム化合物を含む場合、Cu又はCoを含む金属膜に対する洗浄性能により優れることが確認された(実施例44と実施例45との比較)。
化合物群C:モノエタノールアミン、2-(メチルアミノ)-2-メチル-1-プロパノール、ジエタノールアミン、ジエチレングリコールアミン、トリスヒドロキシメチルアミノメタン、ピペラジン、N-(2-アミノエチル)ピペラジン、1,4-ビス(2-ヒドロキシエチル)ピペラジン、1,4―ビス(2-アミノエチル)ピペラジン、及び、1,4―ビス(3-アミノプロピル)ピペラジン。
化合物群D:グリコール酸、リンゴ酸、及び、酒石酸。
その後、室温(23℃)に調整した各実施例の洗浄液のサンプルを用いて、バフ研磨処理が施されたウエハを30秒間かけて洗浄し、次いで、乾燥処理した。
得られたウエハの研磨面に対して、上記の評価試験方法に従って洗浄液の洗浄性能及び腐食防止性能を評価したところ、上記の各実施例の洗浄液と同様の評価結果を有することが確認された。
Claims (14)
- 化学機械研磨処理が施された半導体基板用の洗浄液であって、
カルボキシル基を1つ有するアミノ酸である成分Aと、
アミノポリカルボン酸及びポリホスホン酸からなる群より選択される少なくとも1種である成分Bと、
脂肪族アミンである成分C(ただし、前記成分A、前記アミノポリカルボン酸、及び、第4級アンモニウム化合物は除く)とを含み、
前記成分Aの含有量に対する前記成分Bの含有量の質量比が0.2~10であり、
前記成分Aの含有量と前記成分Bの含有量との和に対する前記成分Cの含有量の質量比が5~100である、
洗浄液。 - 前記成分Aが、グリシン、ヒスチジン、システイン、アルギニン、メチオニン、サルコシン及びアラニンからなる群より選択される少なくとも1種を含む、請求項1に記載の洗浄液。
- 前記成分Bが、ジエチレントリアミン五酢酸、エチレンジアミン四酢酸、トランス-1,2-ジアミノシクロヘキサン四酢酸、ニトリロトリス(メチレンホスホン酸)及びエチレンジアミンテトラ(メチレンホスホン酸)からなる群より選択される少なくとも1種を含む、請求項1又は2に記載の洗浄液。
- 前記成分Cが、アミノアルコールを含む、請求項1~3のいずれか1項に記載の洗浄液。
- 含窒素へテロ芳香族化合物、還元剤、アニオン性界面活性剤、並びに、キレート剤(ただし、前記成分A、前記成分B及び前記成分Cに含まれる化合物は除く)からなる群より選択される少なくとも1種である成分Dを更に含む、請求項1~4のいずれか1項に記載の洗浄液。
- 前記成分Aの含有量と前記成分Bの含有量との和に対する前記成分Dの含有量の質量比が0.1~20である、請求項5に記載の洗浄液。
- 第4級アンモニウムカチオンを有する化合物又はその塩である第4級アンモニウム化合物を更に含む、請求項1~6のいずれか1項に記載の洗浄液。
- 前記第4級アンモニウム化合物が有する前記第4級アンモニウムカチオンが非対称構造を有する、請求項7に記載の洗浄液。
- 2種以上の前記第4級アンモニウム化合物を含む、請求項7又は8に記載の洗浄液。
- 2種以上の還元剤を更に含む、請求項1~9のいずれか1項に記載の洗浄液。
- 前記洗浄液のpHが、25℃において8.0~12.0である、請求項1~10のいずれか1項に記載の洗浄液。
- 前記半導体基板が、銅及びコバルトからなる群より選択される少なくとも1種を含む金属膜を有する、請求項1~11のいずれか1項に記載の洗浄液。
- 前記半導体基板が、タングステンを含む金属膜を有する、請求項1~12のいずれか1項に記載の洗浄液。
- 請求項1~13のいずれか1項に記載の洗浄液を、化学機械研磨処理が施された半導体基板に適用して洗浄する工程を含む、半導体基板の洗浄方法。
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WO2023074290A1 (ja) * | 2021-10-29 | 2023-05-04 | 富士フイルム株式会社 | 半導体基板用処理液 |
WO2023189432A1 (ja) * | 2022-03-28 | 2023-10-05 | 富士フイルム株式会社 | 洗浄組成物、半導体基板の製造方法 |
WO2024095923A1 (ja) * | 2022-10-31 | 2024-05-10 | 東京応化工業株式会社 | 洗浄液、及び基板の洗浄方法 |
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