WO2017119334A1 - Liquide de traitement, procédé de nettoyage de substrat et procédé de fabrication de dispositif à semi-conducteur - Google Patents
Liquide de traitement, procédé de nettoyage de substrat et procédé de fabrication de dispositif à semi-conducteur Download PDFInfo
- Publication number
- WO2017119334A1 WO2017119334A1 PCT/JP2016/088670 JP2016088670W WO2017119334A1 WO 2017119334 A1 WO2017119334 A1 WO 2017119334A1 JP 2016088670 W JP2016088670 W JP 2016088670W WO 2017119334 A1 WO2017119334 A1 WO 2017119334A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- treatment liquid
- cleaning
- compound
- substrate
- liquid
- Prior art date
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- 239000007788 liquid Substances 0.000 title claims abstract description 348
- 238000011282 treatment Methods 0.000 title claims abstract description 263
- 238000000034 method Methods 0.000 title claims abstract description 127
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- -1 hydroxylamine compound Chemical class 0.000 claims abstract description 102
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- 239000011668 ascorbic acid Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- JCXKHYLLVKZPKE-UHFFFAOYSA-N benzotriazol-1-amine Chemical compound C1=CC=C2N(N)N=NC2=C1 JCXKHYLLVKZPKE-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 1
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- STIAPHVBRDNOAJ-UHFFFAOYSA-N carbamimidoylazanium;carbonate Chemical compound NC(N)=N.NC(N)=N.OC(O)=O STIAPHVBRDNOAJ-UHFFFAOYSA-N 0.000 description 1
- JYYPXINUNNKCGO-UHFFFAOYSA-N carboxy(ethoxy)carbamic acid Chemical compound CCON(C(O)=O)C(O)=O JYYPXINUNNKCGO-UHFFFAOYSA-N 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- UVSNFZAOYHOOJO-UHFFFAOYSA-N chembl1343456 Chemical compound OC1=CC=C2N=NNC2=C1 UVSNFZAOYHOOJO-UHFFFAOYSA-N 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- SHQSVMDWKBRBGB-UHFFFAOYSA-N cyclobutanone Chemical compound O=C1CCC1 SHQSVMDWKBRBGB-UHFFFAOYSA-N 0.000 description 1
- DCZFGQYXRKMVFG-UHFFFAOYSA-N cyclohexane-1,4-dione Chemical compound O=C1CCC(=O)CC1 DCZFGQYXRKMVFG-UHFFFAOYSA-N 0.000 description 1
- NUUPJBRGQCEZSI-UHFFFAOYSA-N cyclopentane-1,3-diol Chemical compound OC1CCC(O)C1 NUUPJBRGQCEZSI-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- LKLBILXACKXSPD-UHFFFAOYSA-O diethyl(hydroxy)azanium;nitrate Chemical compound [O-][N+]([O-])=O.CC[NH+](O)CC LKLBILXACKXSPD-UHFFFAOYSA-O 0.000 description 1
- KDUGCNOFFAFOLR-UHFFFAOYSA-N diethyl(hydroxy)azanium;sulfate Chemical compound [O-]S([O-])(=O)=O.CC[NH+](O)CC.CC[NH+](O)CC KDUGCNOFFAFOLR-UHFFFAOYSA-N 0.000 description 1
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical compound CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- ZZGUZQXLSHSYMH-UHFFFAOYSA-N ethane-1,2-diamine;propanoic acid Chemical compound NCCN.CCC(O)=O.CCC(O)=O ZZGUZQXLSHSYMH-UHFFFAOYSA-N 0.000 description 1
- BBZQTKQSEQOSKT-UHFFFAOYSA-N ethoxy(sulfo)sulfamic acid Chemical compound CCON(S(O)(=O)=O)S(O)(=O)=O BBZQTKQSEQOSKT-UHFFFAOYSA-N 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- IFQUWYZCAGRUJN-UHFFFAOYSA-N ethylenediaminediacetic acid Chemical compound OC(=O)CNCCNCC(O)=O IFQUWYZCAGRUJN-UHFFFAOYSA-N 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- PKWIYNIDEDLDCJ-UHFFFAOYSA-N guanazole Chemical compound NC1=NNC(N)=N1 PKWIYNIDEDLDCJ-UHFFFAOYSA-N 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- YIVSWULVVGTVFT-UHFFFAOYSA-L hydroxyazanium;oxalate Chemical compound O[NH3+].O[NH3+].[O-]C(=O)C([O-])=O YIVSWULVVGTVFT-UHFFFAOYSA-L 0.000 description 1
- UNFDKMXBKPSFIJ-UHFFFAOYSA-N hydroxylamine;hydrofluoride Chemical compound F.ON UNFDKMXBKPSFIJ-UHFFFAOYSA-N 0.000 description 1
- XBUFCZMOAHHGMX-UHFFFAOYSA-N hydroxylamine;phosphoric acid Chemical compound ON.ON.ON.OP(O)(O)=O XBUFCZMOAHHGMX-UHFFFAOYSA-N 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- 229940102253 isopropanolamine Drugs 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- 150000007522 mineralic acids Chemical class 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
- OKQVTLCUHATGDD-UHFFFAOYSA-N n-(benzotriazol-1-ylmethyl)-2-ethyl-n-(2-ethylhexyl)hexan-1-amine Chemical compound C1=CC=C2N(CN(CC(CC)CCCC)CC(CC)CCCC)N=NC2=C1 OKQVTLCUHATGDD-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
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- AQFWNELGMODZGC-UHFFFAOYSA-N o-ethylhydroxylamine Chemical compound CCON AQFWNELGMODZGC-UHFFFAOYSA-N 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- ZHZCYWWNFQUZOR-UHFFFAOYSA-N pent-4-en-2-ol Chemical compound CC(O)CC=C ZHZCYWWNFQUZOR-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 150000003482 tantalum compounds Chemical class 0.000 description 1
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 1
- MAKDTFFYCIMFQP-UHFFFAOYSA-N titanium tungsten Chemical compound [Ti].[W] MAKDTFFYCIMFQP-UHFFFAOYSA-N 0.000 description 1
- MPSUGQWRVNRJEE-UHFFFAOYSA-N triazol-1-amine Chemical compound NN1C=CN=N1 MPSUGQWRVNRJEE-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 1
- IJGSGCGKAAXRSC-UHFFFAOYSA-M tris(2-hydroxyethyl)-methylazanium;hydroxide Chemical compound [OH-].OCC[N+](C)(CCO)CCO IJGSGCGKAAXRSC-UHFFFAOYSA-M 0.000 description 1
- JABYJIQOLGWMQW-UHFFFAOYSA-N undec-4-ene Chemical compound CCCCCCC=CCCC JABYJIQOLGWMQW-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Images
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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/10—Salts
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/26—Organic compounds containing oxygen
-
- 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
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02041—Cleaning
- H01L21/02043—Cleaning before device manufacture, i.e. Begin-Of-Line process
- H01L21/02052—Wet cleaning only
-
- 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
- H01L21/02079—Cleaning for reclaiming
-
- 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
- Patent Document 1 discloses that a composition containing water, a hydroxylamine salt compound, and a corrosion inhibitor is used as the treatment liquid (claim 1 and the like).
- Cleaning step D for cleaning A drainage recovery step E for recovering the drainage used in the cleaning step D; Further comprising The substrate cleaning method according to [9], wherein the cleaning step D and the drainage recovery step E are repeatedly performed to recycle the drainage.
- the triazole compound examples include a triazole compound having a benzene ring structure (that is, a benzotriazole compound), a triazole compound having no benzene ring structure, and the like.
- the treatment liquid preferably contains at least one compound selected from benzotriazole, carboxybenzotriazole, 5-methyl-benzotriazole, and triazole from the viewpoint of further improving the anticorrosion performance, and 5-methyl- More preferably, it contains benzotriazole.
- the number of objects having a size of 0.05 ⁇ m or more contained in the treatment liquid of the present invention is 1 to 2000, preferably 1 to 1000, and more preferably 1 to 400.
- the number is more preferably 1 or more and less than 300, and particularly preferably 1 to 100.
- the residue removal performance and anticorrosion performance of the treatment liquid are excellent, and the residue removal performance and corrosion prevention performance of the treatment liquid after repeated environmental temperature changes are excellent. It will be a thing.
- the residue removal performance and the anticorrosion performance of the treatment liquid are insufficient, or the anticorrosion performance of the treatment liquid after repeated environmental temperature changes is insufficient. It becomes.
- the number of the objects to be counted is more than 2000, the anticorrosion performance of the treatment liquid becomes insufficient, or the residue removal performance and anticorrosion performance of the treatment liquid after repeated environmental temperature changes are insufficient. It becomes.
- DTPA diethylenetriaminepentaacetic acid
- EDTA ethylenediaminetetraacetic acid
- trans-1,2-diaminocyclohexanetetraacetic acid are preferable. These compounds can be blended alone or in combination of two or more.
- water-soluble alcohol examples include alkane diol (for example, including alkylene glycol), alkoxy alcohol (for example, including glycol monoether), saturated aliphatic monohydric alcohol, unsaturated non-aromatic monohydric alcohol, and ring.
- alkane diol for example, including alkylene glycol
- alkoxy alcohol for example, including glycol monoether
- saturated aliphatic monohydric alcohol unsaturated non-aromatic monohydric alcohol
- ring A low molecular weight alcohol containing a structure is mentioned.
- alkoxy alcohol examples include 3-methoxy-3-methyl-1-butanol, 3-methoxy-1-butanol, 1-methoxy-2-butanol, and water-soluble glycol monoether.
- glycol monoether examples include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n-propyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol.
- water-soluble ketones include acetone, propanone, cyclobutanone, cyclopentanone, cyclohexanone, diacetone alcohol, 2-butanone, 5-hexanedione, 1,4-cyclohexanedione, 3-hydroxyacetophenone, 1,3-cyclohexane.
- Examples include dione and cyclohexanone.
- Water-soluble esters include glycol monoesters such as ethyl acetate, ethylene glycol monoacetate, diethylene glycol monoacetate, and propylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol Examples include glycol monoether monoesters such as monoethyl ether acetate. Among these, ethylene glycol monobutyl ether, tri (propylene glycol) methyl ether, and diethylene glycol monoethyl ether are preferable.
- water-soluble organic solvents water-soluble alcohols are preferable, alkanediols, glycols, and alkoxy alcohols are more preferable, and alkoxy alcohols are particularly preferable from the viewpoint of further improving the corrosion prevention effect.
- the water-soluble organic solvents may be used alone or in combination of two or more.
- the pH of the treatment liquid of the present invention is not particularly limited, but is preferably not less than pKa of hydroxylamine and a conjugate acid of hydroxylamine salt. Residue removal performance is dramatically improved by being pKa or more of the conjugate acid of hydroxylamine and hydroxylamine salt. In other words, when the ratio of hydroxylamine and hydroxylamine salt present in the molecular state in the treatment liquid is large, the effect of the present invention is remarkably obtained. For example, the pKa of hydroxylamine conjugate acid is about 6.
- the treatment liquid of the present invention is preferably adjusted to pH 3-11. In order to bring the pH of the treatment liquid into the above range, it is desirable that the treatment liquid contains a pH adjusting agent. When the pH of the treatment liquid is within the above range, both the corrosion rate and the residue removal performance are more excellent. As a measuring method of pH, it can measure using a well-known pH meter.
- the treatment liquid of the present invention may contain quaternary ammonium hydroxides.
- residue removal performance can be further improved, and it can also function as a pH adjuster.
- the quaternary ammonium hydroxide is preferably a compound represented by the following general formula (4).
- R 4A to R 4D each independently represent an alkyl group having 1 to 6 carbon atoms (for example, methyl group, ethyl group, butyl group, etc.), or a hydroxyalkyl group having 1 to 6 carbon atoms (for example, A hydroxymethyl group, a hydroxyethyl group, a hydroxybutyl group, etc.), a benzyl group, or an aryl group (for example, a phenyl group, a naphthyl group, a naphthalene group, etc.). Of these, an alkyl group, a hydroxyethyl group, and a benzyl group are preferable.
- tetramethylammonium hydroxide tetraethylammonium hydroxide
- benzyltrimethylammonium hydroxide choline
- Quaternary ammonium hydroxides may be used alone or in combination of two or more.
- the content of the quaternary ammonium hydroxide in the treatment liquid is preferably 0.1 to 15% by mass, and preferably 0.5 to 10% by mass with respect to the total mass of the treatment liquid of the present invention. Is more preferably 0.5 to 5% by mass.
- alkanolamines In the treatment liquid, solubilization of additive components and organic residue may be promoted, and alkanolamines may be contained from the viewpoint of preventing corrosion.
- the alkanolamines may be any of primary amines, secondary amines, and tertiary amines, and are preferably monoamines, diamines, or triamines, and more preferably monoamines.
- the alkanol group of the amine preferably has 1 to 5 carbon atoms.
- a compound represented by the following formula (5) is preferable.
- alkanolamines include monoethanolamine, diethanolamine, triethanolamine, tert-butyldiethanolamine, isopropanolamine, 2-amino-1-propanol, 3-amino-1-propanol, isobutanolamine, 2 -Amino-2-ethoxy-propanol, and 2-amino-2-ethoxy-ethanol, also known as diglycolamine.
- Alkanolamines may be used alone or in combination of two or more.
- the content of alkanolamines in the treatment liquid is preferably 0.1 to 80% by mass, more preferably 0.5 to 50% by mass, based on the total mass of the treatment liquid of the present invention. More preferably, the content is 0.5 to 20% by mass.
- the treatment liquid of the present invention may contain other additives as long as the effects of the present invention are achieved.
- other additives include surfactants and antifoaming agents.
- the treatment liquid in the present invention can be stored, transported and used in any container as long as corrosivity is not a problem (regardless of whether it is a kit or not).
- a container a container having a high cleanliness and a small amount of impurity elution is preferable for semiconductor applications.
- the containers that can be used include, but are not limited to, “Clean Bottle” series manufactured by Aicero Chemical Co., Ltd., “Pure Bottle” manufactured by Kodama Resin Co., Ltd., and the like.
- the inner wall of the container or its container is subjected to a resin different from one or more resins selected from the group consisting of polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin, or a rust prevention / metal elution prevention treatment.
- a resin different from one or more resins selected from the group consisting of polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin, or a rust prevention / metal elution prevention treatment.
- a fluorine-based resin perfluoro resin
- the processing liquid of the present invention is not particularly limited with respect to its production method. It can manufacture by fully mixing a predetermined raw material using stirrers, such as a mixing mixer. Moreover, the method of mixing after preparing to preset pH previously, or the method of adjusting to preset pH after mixing can be used. Furthermore, it is also possible to use a method in which a concentrated solution containing the above compound is produced and diluted to a predetermined concentration at the time of use. Moreover, it can also be used by adjusting the concentrated solution to a set pH after dilution. A predetermined amount of pure water for dilution can be added to the concentrate, and a predetermined amount of concentrate can be added to the pure water for dilution.
- the treatment liquid of the present invention is for mixing a predetermined raw material and then counting the number of objects to be counted having a size of 0.05 ⁇ m or more, which is counted by a light scattering type liquid particle counter, per ml. It is preferable to have a process.
- examples of the object to be cleaned in the substrate cleaning method of the present invention include a laminate including a metal film, an interlayer insulating film, and a metal hard mask on the substrate at least in this order.
- the laminate further has a hole formed from the surface (opening) of the metal hard mask toward the substrate so as to expose the metal film surface through a dry etching process or the like.
- the manufacturing method of the laminate having holes as described above is not particularly limited, but is usually a pre-treatment laminate having a substrate, a metal film, an interlayer insulating film, and a metal hard mask in this order.
- FIG. 1 the cross-sectional schematic diagram which shows an example of the laminated body which is the washing
- a laminate 10 shown in FIG. 1 includes a metal film 2, an etching stopper layer 3, an interlayer insulating film 4, and a metal hard mask 5 in this order on a substrate 1, and a metal film at a predetermined position after a dry etching process or the like.
- a hole 6 through which 2 is exposed is formed. That is, the object to be cleaned shown in FIG. 1 includes a substrate 1, a metal film 2, an etching stop layer 3, an interlayer insulating film 4, and a metal hard mask 5 in this order, and an opening of the metal hard mask 5.
- the wiring material for forming the metal film is not particularly limited, and examples thereof include metals, metal nitrides, and alloys. Specific examples include copper, titanium, titanium-tungsten, titanium nitride, tungsten, cobalt, tantalum, tantalum compounds, chromium, chromium oxide, and aluminum. From the viewpoint of enjoying the effect of the treatment liquid of the present invention, cobalt and tungsten are particularly desirable as the wiring material.
- the component having a large amount of impurities at the time of the raw material it is preferable to use a component that has been subjected to foreign substance removal by filtering and ion component reduction by an ion exchange resin or the like. Furthermore, it is preferable to perform the above-described processing such as filtering so that the number of the objects to be counted included in the processing liquid falls within a desired range.
- the substrate cleaning method of the present invention may further include, after the cleaning step B, a step of rinsing the substrate with a mask with a solvent (rinsing step B2).
- the rinsing step B2 is preferably performed continuously with the cleaning step B and is a rinsing step with a rinsing solvent for 5 seconds to 5 minutes.
- the rinsing step B2 may be performed using the mechanical stirring method described above.
- the rinsing solvent ammonium hydroxide aqueous solution, DI water, methanol, ethanol and isopropyl alcohol are preferable, ammonium hydroxide aqueous solution, DI water and isopropyl alcohol are more preferable, and ammonium hydroxide aqueous solution and DI water are preferable. Further preferred.
- a method for bringing the rinsing solvent into contact with the substrate with mask the above-described method for bringing the treatment liquid into contact with the substrate with mask can be similarly applied.
- the temperature of the rinsing solvent in the rinsing step B2 is preferably 16 to 27 ° C. You may use the process liquid mentioned above as a rinse solvent of rinse process B2.
- a cleaning step D for cleaning a substrate comprising: A drainage recovery step E for recovering the drainage of the processing liquid used in the cleaning step D, and The washing step D and the drainage recovery step E are repeatedly performed.
- the cleaning process D for cleaning the substrate using the collected drainage of the processing liquid is synonymous with the cleaning process B in the above-described aspect, and the preferable aspect is also the same.
- the drainage recovery means in the drainage recovery steps C and E is not particularly limited.
- the collected waste liquid is preferably stored in the above-described resin container in the above-described static elimination process J, and at this time, a static elimination process similar to that in the static elimination process J may be performed.
- HA Hydroxylamine (BASF)
- HAS hydroxylammonium sulfate (manufactured by BASF)
- HAC hydroxylammonium hydrochloride (manufactured by Wako Pure Chemical Industries, Ltd.)
- HAN hydroxylammonium nitrate (manufactured by Sigma-Aldrich)
- the etching solutions of the TiO 2 film were performed using the respective treatment liquids of Examples and Comparative Examples within 24 hours after preparation. Specifically, by immersing the TiO 2 film 5 minutes in the treatment liquid of the examples and comparative examples, on the basis of the thickness difference of the TiO 2 film before and after immersion in the processing solution, the etching rate ( ⁇ / min) Calculated.
- the film thickness of the TiO 2 film before and after the treatment was measured using an ellipsometry (spectral ellipsometer, trade name “Vase”, manufactured by JA Woollam Japan Co., Ltd.) with a measurement range of 250 to 1000 nm and a measurement angle of 70.
- etching rate (ER) of the TiO 2 film was evaluated according to the following evaluation criteria.
- thermocycle test Evaluation of residue removal performance after thermocycle test
- Each treatment solution was sealed in a container (clean bottle made by Aicello Chemical).
- one cycle is to leave the container filled with the treatment liquid under the condition of 12 hours at 5 ° C., and then leave the container filled with the treatment liquid under the condition of 12 hours at 30 ° C.
- a thermocycle test was repeated 90 times.
- the thermocycle test in the Example column is a test corresponding to repeated temperature environment changes.
- an evaluation test of the residue removal performance was performed in the same procedure as the above "(a) Evaluation of residue removal performance within 24 hours after preparation”.
- the evaluation criteria are the same as in the above “(a) Evaluation of residue removal performance within 24 hours after preparation”.
- the concentration of Fe ions contained in the treatment liquid is within the range of 10 mass ppt to 1000 mass ppb (Examples 17, 18, 21, and 22)
- the residue removal performance after long-term refrigerated storage is excellent. Indicated.
- the Fe ion concentration contained in the treatment liquid is in the range of 10 mass ppt or more and less than 1000 mass ppt (Examples 17 and 21)
- the content ratio (mass ratio) of the mercapto group-containing compound to the triazole compound contained as a corrosion inhibitor in the treatment liquid is 0.1. It was shown that the residue removal performance and anticorrosion performance after long-term refrigerated storage were further improved by being in the range of ⁇ 50 (Examples 26, 27, and 28). Further, it was shown that the residue removal performance and anticorrosion performance after long-term refrigerated storage were further improved when the content ratio was in the range of 0.1 to 20 (Examples 26 and 27). Furthermore, it was shown that when the content ratio is in the range of 0.1 to 10 (Example 26), the residue removal performance and anticorrosion performance after long-term refrigeration storage are further improved.
- the residue removal performance did not change for each of the treatment liquids when it passed through the above-described charge removal step and when it did not.
- the anticorrosion performance of the Co film, the anticorrosion performance of the W film, and the anticorrosion performance of the SiOx film the anticorrosion performance is better when the neutralization process is performed than when the neutralization process is not performed. Obtained. From this result, it was found that the anti-corrosion performance of the treatment liquid was more excellent by passing through the static elimination step.
- the treatment liquid of Example 20 when the recycle test was performed, the residue removal performance and the anticorrosion performance of the Co film and the W film were “B”, which was the same as the case where the recycle test was not performed. Results were obtained. From these results, it has been found that the treatment liquid of the present invention can suppress a decrease in performance and is excellent in recyclability even when a substrate is repeatedly treated.
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Abstract
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JP2017560115A JP6542393B2 (ja) | 2016-01-05 | 2016-12-26 | 処理液、基板の洗浄方法および半導体デバイスの製造方法 |
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Cited By (5)
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JPWO2017119244A1 (ja) * | 2016-01-05 | 2018-10-25 | 富士フイルム株式会社 | 処理液、基板の洗浄方法、および、半導体デバイスの製造方法 |
WO2019021741A1 (fr) * | 2017-07-28 | 2019-01-31 | 株式会社Screenホールディングス | Procédé de neutralisation de liquide de traitement, procédé de traitement de substrat, et système de traitement de substrat |
JP2021034549A (ja) * | 2019-08-23 | 2021-03-01 | 東京応化工業株式会社 | 充填剤、基板の処理方法、及び充填剤の製造方法 |
WO2022176663A1 (fr) * | 2021-02-22 | 2022-08-25 | 富士フイルム株式会社 | Liquide de nettoyage et procédé de nettoyage d'un substrat semi-conducteur |
JP7288511B2 (ja) | 2019-08-23 | 2023-06-07 | 富士フイルム株式会社 | 洗浄剤組成物 |
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JP6542393B2 (ja) | 2019-07-10 |
KR20180088452A (ko) | 2018-08-03 |
TW201736591A (zh) | 2017-10-16 |
TWI702285B (zh) | 2020-08-21 |
KR102027793B1 (ko) | 2019-10-02 |
JPWO2017119334A1 (ja) | 2018-10-25 |
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