TWI816657B - 清洗組成物及清洗方法 - Google Patents
清洗組成物及清洗方法 Download PDFInfo
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- TWI816657B TWI816657B TW107104759A TW107104759A TWI816657B TW I816657 B TWI816657 B TW I816657B TW 107104759 A TW107104759 A TW 107104759A TW 107104759 A TW107104759 A TW 107104759A TW I816657 B TWI816657 B TW I816657B
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- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 238000000572 ellipsometry Methods 0.000 description 1
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- AFAXGSQYZLGZPG-UHFFFAOYSA-N ethanedisulfonic acid Chemical compound OS(=O)(=O)CCS(O)(=O)=O AFAXGSQYZLGZPG-UHFFFAOYSA-N 0.000 description 1
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- 229940116333 ethyl lactate Drugs 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- WCASXYBKJHWFMY-UHFFFAOYSA-N gamma-methylallyl alcohol Natural products CC=CCO WCASXYBKJHWFMY-UHFFFAOYSA-N 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000007788 liquid 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
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 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
- 230000000873 masking effect Effects 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910001509 metal bromide Inorganic materials 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- OOHAUGDGCWURIT-UHFFFAOYSA-N n,n-dipentylpentan-1-amine Chemical compound CCCCCN(CCCCC)CCCCC OOHAUGDGCWURIT-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- WLGDAKIJYPIYLR-UHFFFAOYSA-N octane-1-sulfonic acid Chemical compound CCCCCCCCS(O)(=O)=O WLGDAKIJYPIYLR-UHFFFAOYSA-N 0.000 description 1
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- 235000006408 oxalic acid Nutrition 0.000 description 1
- GSWAOPJLTADLTN-UHFFFAOYSA-N oxidanimine Chemical compound [O-][NH3+] GSWAOPJLTADLTN-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
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- ZHZCYWWNFQUZOR-UHFFFAOYSA-N pent-4-en-2-ol Chemical compound CC(O)CC=C ZHZCYWWNFQUZOR-UHFFFAOYSA-N 0.000 description 1
- JGTNAGYHADQMCM-UHFFFAOYSA-N perfluorobutanesulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F JGTNAGYHADQMCM-UHFFFAOYSA-N 0.000 description 1
- QZHDEAJFRJCDMF-UHFFFAOYSA-N perfluorohexanesulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F QZHDEAJFRJCDMF-UHFFFAOYSA-N 0.000 description 1
- YFSUTJLHUFNCNZ-UHFFFAOYSA-N perfluorooctane-1-sulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YFSUTJLHUFNCNZ-UHFFFAOYSA-N 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- NIXKBAZVOQAHGC-UHFFFAOYSA-N phenylmethanesulfonic acid Chemical compound OS(=O)(=O)CC1=CC=CC=C1 NIXKBAZVOQAHGC-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- JLKDVMWYMMLWTI-UHFFFAOYSA-M potassium iodate Chemical compound [K+].[O-]I(=O)=O JLKDVMWYMMLWTI-UHFFFAOYSA-M 0.000 description 1
- 239000001230 potassium iodate Substances 0.000 description 1
- 229940093930 potassium iodate Drugs 0.000 description 1
- 235000006666 potassium iodate Nutrition 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
- WHMDPDGBKYUEMW-UHFFFAOYSA-N pyridine-2-thiol Chemical compound SC1=CC=CC=N1 WHMDPDGBKYUEMW-UHFFFAOYSA-N 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 235000012239 silicon dioxide Nutrition 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
- 238000002791 soaking Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- LZOZLBFZGFLFBV-UHFFFAOYSA-N sulfene Chemical compound C=S(=O)=O LZOZLBFZGFLFBV-UHFFFAOYSA-N 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- 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
- LUVHDTDFZLTVFM-UHFFFAOYSA-M tetramethylazanium;chlorate Chemical compound [O-]Cl(=O)=O.C[N+](C)(C)C LUVHDTDFZLTVFM-UHFFFAOYSA-M 0.000 description 1
- FDXKBUSUNHRUIZ-UHFFFAOYSA-M tetramethylazanium;chlorite Chemical compound [O-]Cl=O.C[N+](C)(C)C FDXKBUSUNHRUIZ-UHFFFAOYSA-M 0.000 description 1
- ZRVXFJFFJZFRLQ-UHFFFAOYSA-M tetramethylazanium;iodate Chemical compound [O-]I(=O)=O.C[N+](C)(C)C ZRVXFJFFJZFRLQ-UHFFFAOYSA-M 0.000 description 1
- ZCWKIFAQRXNZCH-UHFFFAOYSA-M tetramethylazanium;perchlorate Chemical compound C[N+](C)(C)C.[O-]Cl(=O)(=O)=O ZCWKIFAQRXNZCH-UHFFFAOYSA-M 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910021655 trace metal ion Inorganic materials 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 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
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000003021 water soluble solvent Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/042—Acids
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- 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
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/044—Hydroxides or bases
-
- 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
- C11D3/166—Organic compounds containing borium
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
-
- 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
- C11D3/34—Organic compounds containing sulfur
- C11D3/3409—Alkyl -, alkenyl -, cycloalkyl - or terpene sulfates or sulfonates
-
- 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
- C11D3/43—Solvents
-
- 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
- C11D7/06—Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/08—Acids
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic 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
- C11D7/50—Solvents
- C11D7/5004—Organic solvents
- C11D7/5009—Organic solvents containing phosphorus, sulfur or silicon, e.g. dimethylsulfoxide
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/50—Solvents
- C11D7/5004—Organic solvents
- C11D7/5022—Organic solvents containing oxygen
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02041—Cleaning
- H01L21/02057—Cleaning during device manufacture
- H01L21/0206—Cleaning during device manufacture during, before or after processing of insulating layers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02041—Cleaning
- H01L21/02057—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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02041—Cleaning
- H01L21/02057—Cleaning during device manufacture
- H01L21/02068—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers
- H01L21/02071—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers the processing being a delineation, e.g. RIE, of conductive layers
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- C11D2111/22—
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- Power Engineering (AREA)
- Emergency Medicine (AREA)
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Abstract
這揭示係有關於一清洗組成物,其包含:1)至少一氧化還原劑;2)至少一有機溶劑,其選自於由水溶性醇、水溶性酮、水溶性酯、水溶性碸及水溶性醚構成之群組;3)至少一含硼化合物,其選自於由硼酸、
Description
本申請案主張2017年2月10日申請之美國暫時申請案第62/457,293號的優先權,該申請案在此全部加入作為參考。
本揭示係有關於用於半導體基材之新清洗組成物及清洗半導體基材之新方法。更詳而言之,本揭示係有關於在電漿蝕刻沉積在該等基材上之金屬層或介電材料層後用於半導體基材及在透過一電漿灰化程序移除整體抗蝕層後移除留在該等基材上之殘留物的清洗組成物。
在製造積體電路裝置時,使用光阻作為一中間遮罩,用以藉由一連串光刻法及電漿蝕刻步驟將一倍縮光罩(reticle)之初始遮罩圖案轉印至晶圓基材上。在該積體電路裝置製程中之其中一主要步驟係由該晶圓基材移除圖案化之光阻膜。通常,這步驟係藉由兩種方法中之一種來實施。
一方法包含使覆蓋光阻之基材與一光阻剝除溶液接觸的一濕剝除步驟,且該光阻剝除溶液主要由一
有機溶劑及一胺構成。但是,該等剝除溶液通常無法完全地且可靠地移除該等光阻膜,特別是在該等光阻膜在製造時已暴露於UV輻射及電漿處理後。某些光阻膜會因該等處理而高度交聯且更難以溶解在一剝除溶液中。此外,在這些習知濕剝除方法中使用之化學藥品有時無法有效地移除在用含鹵素氣體電漿蝕刻金屬或氧化物層時形成的無機或有機金屬殘留材料。
移除一光阻膜之另一方法包含使一塗覆光阻之晶圓暴露於以氧為主之電漿以便在一稱為電漿灰化之程序中由該基材燒去該抗蝕膜。但是,電漿灰化亦無法完全有效地移除上述電漿蝕刻副產物。相反地,通常藉由使該處理之金屬及介電薄膜接著暴露於某些清洗溶液來移除這些電漿蝕刻副產物。
含金屬基材通常容易受到腐蝕。例如,如鋁、銅、鋁銅合金、氮化鎢、鎢(W)、鈷(Co)、二氧化鈦、其他金屬及金屬氮化物之基材會輕易地腐蝕。此外,藉由使用習知清洗化學藥品可蝕刻在該積體電路電路中之介電體(例如,層間介電體或超低k介電體)。另外,隨著該裝置幾何形狀縮小,該積體電路裝置製造商可忍受之腐蝕量亦越來越小。
同時,由於殘留物變得越來越難移除且必須控制腐蝕至更低程度,清洗溶液應可安全使用且對環境友善。
因此,該清洗溶液應可有效地移除電漿蝕刻
及電漿灰化殘留物且亦應對全部暴露之基材材料無腐蝕性。
本揭示係有關於無腐蝕性清洗組成物,其可使用於由一半導體基材移除殘留物(例如,電漿蝕刻及/或電漿灰化殘留物)作為一多步驟製造程序中之一中間步驟。這些殘留物包括各種比較不可溶之有機化合物的混合物,例如殘留光阻;有機金屬化合物;如鋁氧化物(AlOx)、鈦氧化物(TiOx)、鋯氧化物(ZrOx)、鉭氧化物(TaOx)及鉿氧化物(HfOx)等之金屬氧化物(可形成為來自暴露金屬之反應副產物);如鋁(Al)、鋁/銅合金、銅(Cu)、鈦(Ti)、鉭(Ta)、鎢(W)及鈷(Co)等之金屬;如鋁氮化物(AlN)、鋁氧氮化物(AlOxNy)、鈦氮化物(TiN)、鉭氮化物(TaN)及鎢氮化物(WN)等之金屬氮化物;其合金;及其他材料。在此所述之清洗組成物的一優點係它可清洗多種遭遇之殘留物且通常對暴露之基材材料(例如,暴露之金屬(如鋁、鋁/銅合金、銅、鈦、鉭、鎢及鈷),金屬氮化物(如鈦、鉭及鎢氮化物)及其合金)大致無腐蝕性。
在一態樣中,本揭示之特徵為一種清洗組成物,其包含:1)至少一氧化還原劑;2)至少一有機溶劑,其選自於由水溶性醇、水溶性酮、水溶性酯、水溶性碸及水溶性醚構成之群組;
3)至少一含硼化合物,其選自於由硼酸、酸(boronic acids)及其鹽類構成之群組;及4)水。
本揭示之特徵亦為一種由一半導體基材清洗殘留物之方法。該方法包括使包含後蝕刻殘留物及/或後灰化殘留物之一半導體基材與在此所述之一清洗組成物接觸。例如,該方法可包括以下步驟:(A)提供包含後蝕刻殘留物及/或後灰化殘留物的一半導體基材;(B)使該半導體基材與在此所述之一清洗組成物接觸;(C)用一適當沖洗溶劑沖洗該半導體基材;及(D)選擇地,藉由移除該沖洗溶劑且不會破壞該半導體基材之完整性的任何方式乾燥該半導體基材。
如在此定義地,除非另外聲明,應了解的是全部所述百分比為相對於該清洗組成物之總重的重量百分比。除非另外聲明,室溫係定義為在攝氏大約16與大約27度(℃)之間,例如25℃。
該等用語「層」及「膜」可互換地使用。
如在此定義地,一「水溶性」物質(例如,一水溶性醇、酮、酯、碸或醚)表示在25℃之水中具有至少5重量%之一溶解度的一物質。
本揭示之一實施例係有關於一非腐蝕性清
洗組成物,其包括:1)至少一氧化還原劑;2)至少一有機溶劑,其選自於由水溶性醇、水溶性酮、水溶性酯、水溶性碸及水溶性醚構成之群組;3)至少一含硼化合物,其選自於由硼酸、酸及其鹽類構成之群組;及4)水。
通常,這揭示之清洗組成物包含至少一氧化還原劑,吾人相信該至少一氧化還原劑有助於溶解在該半導體表面上之殘留物,例如光阻殘留物、金屬殘留物及金屬氧化物殘留物。在此使用之用語「氧化還原劑」表示在一半導體清洗程序中可產生一氧化及/或一還原的一化合物。一適當氧化還原劑例係羥胺。在某些實施例中,在此所述之氧化還原劑或該清洗組成物未包括一過氧化物(例如,過氧化氫)。
在某些實施例中,這揭示之組成物包括至少大約0.5重量%(例如,至少大約1重量%、至少大約2重量%、至少大約3重量%或至少大約5重量%)及/或至多大約20重量%(例如,至多大約17重量%、至多大約15重量%、至多大約12重量%或至多大約10重量%)之氧化還原劑。
這揭示之組成物包含至少一(例如,二、三、四或四以上)有機溶劑,該至少一有機溶劑選自於由水溶性醇、水溶性酮、水溶性酯、水溶性碸及水溶性醚(例如,二醇二醚)構成之群組。
水溶性醇之種類包括,但不限於:烷烴二醇(包括,但不限於:烷二醇)、二醇、烷氧醇(包括,但不限於:二醇一醚)、飽和脂族一羥醇、不飽和非芳族一羥醇及包含一環結構之低分子量醇(例如,具有低於500g/mol、400g/mol、300g/mol、200g/mol或100g/mol之分子量者)。
水溶性烷烴二醇之例子包括,但不限於:2-甲基-1,3-丙二醇、1,3-丙二醇、2,2-二甲基-1,3-丙二醇、1,4-丁二醇、1,3-丁二醇、1,2-丁二醇、2,3-丁二醇、2,3-二甲基-2,3-丁二醇及烷二醇。
水溶性烷二醇之例子包括,但不限於:乙二醇、丙二醇、己二醇、二乙二醇、二丙二醇、三乙二醇及四乙二醇。
水溶性烷氧醇之例子包括,但不限於:3-甲氧-3-甲基-1-丁醇、3-甲氧-1-丁醇、1-甲氧-2-丁醇及水溶性烷二醇一醚。
水溶性烷二醇一醚之例子包括,但不限於:乙二醇一甲醚、乙二醇一乙醚、乙二醇一正丙醚、乙二醇一異丙醚、乙二醇一正丁醚、二乙二醇一甲醚、二乙二醇一乙醚、二乙二醇一丁醚、三乙二醇一甲醚、三乙二醇一乙醚、三乙二醇一丁醚、1-甲氧-2-丙醇、2-甲氧-1-丙醇、1-乙氧-2-丙醇、2-乙氧-1-丙醇、丙二醇一正丙醚、二丙二醇一甲醚、二丙二醇一乙醚、二丙二醇一正丙醚、三丙二醇一乙醚、三丙二醇一甲醚、乙二醇一苄醚及二乙二醇一苄醚。
水溶性飽和脂族一羥醇之例子包括,但不限於:甲醇、乙醇、正丙醇、異丙醇、1-丁醇、2-丁醇、異丁醇、三級丁醇、2-戊醇、三級戊醇及1-己醇。
水溶性不飽和非芳族一羥醇之例子包括,但不限於:烯丙醇、炔丙醇、2-丁烯醇、3-丁烯醇及4-戊烯-2-醇。
包含一環結構之水溶性低分子量醇的例子包括,但不限於:四氫糠醇、糠醇及1,3-環戊二醇。
水溶性酮之例子包括,但不限於:醋酮、丙酮、環丁酮、環戊酮、環己酮、二丙酮醇、2-丁酮、2,5-己二酮、1,4-環己二酮、3-羥苯乙酮、1,3-環己二酮及環己酮。
水溶性酯之例子包括,但不限於:乙酸乙酯;如乙二醇一乙酸酯、二乙二醇一乙酸酯之二醇一酯;及如丙二醇一甲醚乙酸酯、乙二醇一甲醚乙酸酯、丙二醇一乙醚乙酸酯及乙二醇一乙醚乙酸酯之二醇一醚一酯。
水溶性碸之例子包括,但不限於:環丁碸、二甲碸、1,3-丙碸、1,4-丁碸、二甲磺酸丁酯、磺烯、乙甲碸、聯苯碸及甲苯碸。
水溶性醚之例子包括,但不限於:烷氧醇(例如,烷二醇一醚),如上述者。
在某些實施例中,這揭示之清洗組成物包括至少大約60重量%(例如,至少大約65重量%、至少大約70重量%或至少大約75重量%)及/或至多大約95重量%(例
如,至多大約90重量%、至多大約85重量%或至多大約80重量%)之該至少一有機溶劑。
本揭示之清洗組成物更包括水。較佳地,該水去離子且極純,未包含有機污染物且具有大約4至大約17百萬歐姆之一最小電阻。更佳地,該水之電阻係至少17百萬歐姆。
在某些實施例中,這揭示之清洗組成物包括至少大約5重量%(例如,至少大約8重量%、至少大約12重量%或至少大約16重量%)及/或至多大約28重量%(例如,至多大約24重量%、至多大約20重量%或至多大約18重量%)之水。
在某些實施例中,這揭示之清洗組成物包括至少一含硼化合物。該含硼化合物選自於由硼酸(H3BO3)、酸及其鹽類構成之群組。在某些實施例中,該含硼化合物可為一式(I)之酸:R-B-(OH)2,其中R係C1至C10烷基(例如C1至C4烷基)或芳基(例如,苯基)。一式(I)之酸例係苯基酸。在某些實施例中,硼酸或酸之鹽可為金屬鹽、銨鹽及四烷銨鹽。該等金屬鹽可由一鹼金屬(例如,Li、Na、K、Rb或Cs)或一鹼土金屬(例如,Mg、Ca、Sr或Ba)形成。該四烷銨鹽可包括四甲銨陽離子、四乙銨陽離子、四丙銨陽離子及四丁銨陽離子。
在某些實施例中,這揭示之清洗組成物包括
至少大約0.001重量%(例如,至少大約0.002重量%、至少大約0.005重量%、至少大約0.01重量%、至少大約0.015重量%、至少大約0.02重量%、至少大約0.05重量%或至少大約0.1重量%)及/或至多大約0.2重量%(例如,至多大約0.18重量%、至多大約0.15重量%、至多大約0.12重量%、至多大約0.1重量%或至多大約0.05重量%)之該至少一含硼化合物。在不希望受限於理論之情形下,吾人相信用以上在一清洗組成物中所述量包括該含硼化合物之一清洗組成物可減少該組成物對不希望在該清洗程序中移除之某些暴露基材材料(例如,鈷)的腐蝕效應(例如,藉由降低該清洗組成物對該等暴露基材材料之蝕刻速度)。
這揭示之清洗組成物可選擇地包含至少一添加劑,例如含金屬添加劑及清洗添加劑。
可供該揭示之清洗組成物中使用的含金屬添加劑包括選自於2A族金屬、3B族金屬、4B族金屬、5B族金屬及鑭系金屬之金屬。在某些實施例中,該金屬係Ca、Ba、Ti、Hf、Sr、La、Ce、W、V、Nb或Ta。在某些實施例中,該金屬選自於4B族金屬(例如Ti或Hf)。
該含金屬添加劑可為一金屬鹵化物、一金屬氫氧化物、一金屬溴化物、一金屬烷氧化物、一金屬氧化物或一含金屬銨鹽的形式。在某些實施例中,該含金屬添加劑係一銨鹽。該銨鹽可為一式(I)之鹽:(NH4)mMXn(I);其中m係1、2、3或4;n係1、2、3、4、5或6;M係一金屬離子(例如一2A族金屬、3B族金屬、4B
族金屬、5B族金屬及鑭系金屬之一離子);且X係一鹵離子(例如,F、Cl、Br或I)。在某些實施例中,該含金屬添加劑係六氟鈦酸銨((NH4)2TiF6)。含金屬添加劑之例子可包括鎢硼化物、Ca(OH)2、BaCl2、SrCl2、LaCl3、CeCl3、(NH4)2TiF6、BaTiO3、Ti(OEt)4、Ti(OCH(CH3)2)4、HfO2、V2O5、Nb2O5或TaF3。
在某些實施例中,該含金屬添加劑之量可為該組成物之至少大約0.001重量%(例如,至少大約0.002重量%、至少大約0.004重量%、至少大約0.006重量%、至少大約0.008重量%或至少大約0.01重量%)及/或至多大約0.5重量%(例如,至多大約0.4重量%、至多大約0.3重量%、至多大約0.2重量%、至多大約0.1重量%、至多大約0.08重量%、至多大約0.06重量%、至多大約0.04重量%、至多大約0.02重量%或至多大約0.01重量%)。在不希望受限於理論之情形下,吾人相信用以上在一清洗組成物中所述量包括該含金屬添加劑可減少該組成物之腐蝕效應,即,降低該清洗組成物對不希望在該清洗程序中移除之暴露基材材料(例如,暴露金屬或介電材料)的蝕刻速度。
在某些實施例中,這揭示之清洗組成物可選擇地包含至少一清洗添加劑以增加其清洗能力(例如,移除蝕刻或灰化殘留物)及/或減少其腐蝕效應。在某些實施例中,該清洗添加劑可為一含硫添加劑或一胺基酸。在某些實施例中,該等清洗組成物可包括一含硫添加劑及一胺基酸兩者。
可供該揭示之清洗組成物中使用的含硫添加劑沒有特別限制。在某些實施例中,該含硫添加劑係具有一硫氫基部分(即,SH)或硫醚部分(例如,SR,其中R係C1至C10烷基)之一分子。在某些實施例中,該含硫添加劑可為包含一硫氫基或硫醚部分之一醇、一酸、一胺或一雜環化合物。含硫添加劑例包括,但不限於:3-胺基-5-巰基-1H-1,2,4-三唑;β-巰乙醇;3-胺基-5-甲巰基-1H-1,2,4-三唑;1-苯基-1H-四唑-5-硫醇;4-甲基-4H-1,2,4-三唑-3-硫醇;2-吡啶硫醇;3-巰基丙酸等。在某些實施例中,該含硫添加劑可排除含硫有機酸。
在某些實施例中,該含硫添加劑之量可為該組成物之至少大約0.01重量%(例如,至少大約0.02重量%、至少大約0.04重量%、至少大約0.05重量%、至少大約0.06重量%或至少大約0.08重量%)及/或至多大約0.15重量%(例如,至多大約0.14重量%、至多大約0.12重量%、至多大約0.1重量%、至多大約0.08重量%或至多大約0.07重量%)。在不希望受限於理論之情形下,吾人相信用以上在一清洗組成物中所述量包括該含硫添加劑可增加該組成物用以移除後蝕刻及/或後灰化殘留物之清洗能力及/或降低該清洗組成物對不希望在該清洗程序中移除之暴露基材材料(例如,暴露金屬或介電材料)的蝕刻速度。
在某些實施例中,該清洗添加劑可包括至少一胺基酸(例如,甘胺酸)。該胺基酸可為一自然產生胺基酸或一非自然產生胺基酸(例如,一合成胺基酸)。該胺基
酸可為一D-或L-胺基酸。
在某些實施例中,該胺基酸之量可為該組成物之至少大約0.01重量%(例如,至少大約0.02重量%、至少大約0.04重量%、至少大約0.05重量%、至少大約0.06重量%或至少大約0.08重量%)及/或至多大約0.15重量%(例如,至多大約0.14重量%、至多大約0.12重量%、至多大約0.1重量%、至多大約0.08重量%或至多大約0.07重量%)。在不希望受限於理論之情形下,吾人相信用以上在一清洗組成物中所述量包括該胺基酸可增加該組成物用以移除後蝕刻及/或後灰化殘留物之清洗能力及/或降低該清洗組成物對不希望在該清洗程序中移除之暴露基材材料(例如,暴露金屬或介電材料)的蝕刻速度。
在某些實施例中,這揭示之清洗組成物可包含一或多數有機酸。該等有機酸可在有或沒有上述清洗添加劑(例如,該含硫添加或該胺基酸)存在之情形下在該清洗組成物中使用。可供該揭示之清洗組成物中使用的有機酸包括羧酸及磺酸。可供該揭示之組成物中使用的示範羧酸包括,但不限於:一羧酸、雙羧酸、三羧酸、一羧酸之α-羥酸及β-羥酸、二羧酸之α-羥酸及β-羥酸及三羧酸之α-羥酸及β-羥酸。適當羧酸之例子包括,但不限於:檸檬酸、馬來酸、富馬酸、乳酸、乙醇酸、草酸、酒石酸、琥珀酸及苯甲酸。磺酸之例子包括,但不限於:甲磺酸、三氟甲磺酸、乙磺酸、三氟乙磺酸、全氟乙磺酸、全氟乙氧乙磺酸、全氟甲氧乙磺酸、十二磺酸、全氟十二磺酸、丁
磺酸、全氟丁磺酸、丙磺酸、全氟丙磺酸、辛磺酸、全氟辛磺酸、甲二磺酸、2-甲丙磺酸、環己磺酸、樟腦磺酸、全氟己磺酸、乙二磺酸、苄磺酸、羥苯甲磺酸、萘甲磺酸、降冰片磺酸、苯磺酸、氯苯磺酸、溴苯磺酸、氟苯磺酸、羥苯磺酸、硝苯磺酸、2-羥-5-磺苯甲酸、苯二磺酸、甲苯磺酸(例如,對甲苯磺酸)、甲氯苯磺酸、十二苯磺酸、丁苯磺酸、環己苯磺酸、苦味磺酸、二氯苯磺酸、二溴苯磺酸及2,4,5-三氯苯磺酸。
在某些實施例中,該有機酸之量可為該組成物之至少大約0.01重量%(例如,至少大約0.05重量%、至少大約0.1重量%、至少大約0.12重量%、至少大約0.14重量%、至少大約0.16重量%、至少大約0.18重量%或至少大約0.2重量%)及/或至多大約0.5重量%(例如,至多大約0.4重量%、至多大約0.3重量%、至多大約0.2重量%、至多大約0.18重量%或至多大約0.16重量%)。在不希望受限於理論之情形下,吾人相信該有機酸可作為在該清洗組成物中之一螯合劑以便移除後蝕刻及/或後灰化殘留物。
這揭示之清洗組成物選擇地包含至少一pH調整劑(例如,一酸或一鹼)以便控制pH為大約7至大約11。在某些實施例中,這揭示之組成物可具有至少大約7(例如,至少大約7.5、至少大約8或至少大約8.5)到至多大約11(例如,至多大約10.5、至多大約10、至多大約9.5、至多大約9)之一pH。在不希望受限於理論之情形下,吾人相信具有高於11之一pH的一清洗組成物使該電漿蝕刻殘
留物清洗減少至一無法完成清洗之程度且低於7之一pH會增加某些金屬或介電材料之蝕刻速度至一不必要程度。有效之pH可依據在此所述之組成物中使用的成分種類及量來改變。
如果有的話,所需之該pH調整劑的量可隨著其他成分,特別是羥胺及有機酸在不同調配物中之濃度改變而改變,且隨著使用之特定pH調整劑的分子量改變。通常,該pH調整劑濃度範圍係該清洗組成物重量之大約0.1%至大約3%。在某些實施例中,這揭示之清洗組成物包括至少大約0.1重量%(例如,至少大約0.5重量%、至少大約1重量%或至少大約1.5重量%)及/或至多大約3重量%(例如,至多大約2.5重量%、至多大約2重量%或至多大約1.5重量%)之pH調整劑。
通常,該pH調整劑沒有任何金屬離子(除了微量金屬離子雜質以外)。適當無金屬離子之pH調整劑包括氫氧化銨、四級氫氧化銨、一胺(包括烷醇胺)、二胺、三胺(例如二伸乙三胺五乙酸(DPTA))、亞胺(例如1,8-二吖雙環[5.4.0]-7-十一烯(DBU)及1,5-二吖雙環[4.3.0]-5-壬烯)及胍鹽(例如胍碳酸鹽)。
適當四級氫氧化銨之例子包括,但不限於:氫氧化四甲銨、氫氧化四乙銨、氫氧化四丙銨、氫氧化四丁銨、氫氧化二甲二乙銨、膽鹼、氫氧化四乙醇銨、氫氧化苄三甲銨、氫氧化苄三乙銨及氫氧化苄三丁銨。
適當一胺之例子包括,但不限於:三乙胺、
三丁胺、三戊胺、乙醇胺、二乙醇胺、二乙胺、丁胺、二丁胺及苄胺。
此外,在某些實施例中,本揭示之清洗組成物可包含其他添加劑,例如,另外之pH調整劑、腐蝕抑制劑(例如,一取代或未取代苯并三唑)、界面活性劑、另外之有機溶劑、殺菌劑及去泡劑作為選擇成分。
適當去泡劑之例子包括聚矽氧烷去泡劑(例如,聚二甲基矽氧烷)、聚乙二醇甲醚聚合物、環氧乙烷/環氧丙烷共聚物、及環氧丙基醚封端炔屬二醇乙氧化物(例如在此加入作為參考之美國專利第6,717,019號中所述者)。
在某些實施例中,本揭示之清洗組成物若超過一成分,則可特別以任何組合方式排除該等添加劑成分中之一或多數成分。該等排除之成分係選自於由去氧劑、氫氧化四級銨、胺類、鹼金屬及鹼土金屬鹼(例如NaOH、KOH、LiOH、氫氧化鎂及氫氧化鈣)、一去泡劑以外之界面活性劑、含氟化合物、氧化劑(例如,過氧化物、過氧化氫、硝酸鐵、碘酸鉀、過錳酸鉀、硝酸、亞氯酸銨、氯酸銨、碘酸銨、過硼酸銨、過氯酸銨、過碘酸銨、過硫酸銨、四甲亞氯酸銨、四甲氯酸銨、四甲碘酸銨、四甲過硼酸銨、四甲過氯酸銨、四甲過碘酸銨、四甲過硫酸銨、尿素過氧化氫及過氧乙酸)、研磨劑、矽酸鹽、羥基羧酸、缺少胺基之羧酸及多羧酸、非唑腐蝕抑制劑、胍、胍鹽、無機酸(例如,磺酸、硫酸、亞硫酸、亞硝酸、硝酸、亞磷酸及磷酸)、
吡咯啶酮、聚乙烯吡咯啶酮、金屬鹵化物、式WzMXy之金屬鹵化物,其中W選自於H、一鹼或鹼土金屬及無金屬離子氫氧化物鹼部分;M係選自於由Si、Ge、Sn、Pt、P、B、Au、Ir、Os、Cr、Ti、Zr、Rh、Ru及Sb構成之群組的一金屬;y係4至6;且z係1、2或3、及在這揭示中所述者以外之腐蝕抑制劑。
在某些實施例中,本揭示之清洗組成物未特別地設計成由半導體基材移除整體光阻膜。相反地,本揭示之清洗組成物可設計成在藉由乾或濕剝除方法移除整體抗蝕層後移除全部殘留物。因此,在某些實施例中,本揭示之清洗方法宜在一乾或濕光阻剝除程序後使用。這光阻剝除程序通常在如一蝕刻或植入程序之一圖案轉印程序前實施,或在圖案轉印前完成以修正遮罩誤差。該殘留物之化學成分取決於在該清洗步驟前之程序或多個程序。
可使用任何適當乾剝除程序來由半導體基材移除整體抗蝕層。適當乾剝除程序之例子包括以氧為主之電漿灰化,例如一氟/氧電漿或一N2/H2電漿、臭氧氣相處理、氟電漿處理、熱H2氣體處理(例如在此全部加入作為參考之美國專利第5,691,117號中所述者)等。此外,可使用所屬技術領域中具有通常知識者習知之任何適當習知有機濕剝除溶液來由半導體基材移除整體抗蝕層。
與本揭示之清洗方法一起使用的一較佳剝除程序係一乾剝除程序。較佳地,這乾剝除程序係一以氧為主之電漿灰化程序。該程序藉由在高溫(通常為250℃)
下在真空條件(即,1托耳)下施加一反應性氧環境來由該半導體基材移除大部份之光阻。有機材料藉由這程序氧化且利用程序氣體移除。但是,這程序未由該半導體基材移除無機或有機金屬污染物。通常需要利用本揭示之清洗組成物的該半導體基材之一後續清洗來移除這些殘留物。
在某些實施例中,這揭示之特徵為由一半導體基材清洗殘留物之方法。該等方法可,例如,藉由使包含後蝕刻殘留物及/或後灰化殘留物之一半導體基材與在此所述之一清洗組成物接觸來實施。該方法可更包括在該接觸步驟後藉由一沖洗溶劑沖洗該半導體基材及/或在該沖洗步驟後乾燥該半導體基材。在某些實施例中,該半導體基材可更包括一材料(例如,一暴露材料)或一層材料,其中該材料選自於由Cu、Co、W、AlOx、AlN、AlOxNy、Ti、TiN、Ta、TaN、TiOx、ZrOx、HfOx及TaOx構成之群組。
在某些實施例中,該清洗方法包含以下步驟:(A)提供包含後蝕刻殘留物及/或後灰化殘留物的一半導體基材;(B)使該半導體基材與在此所述之一清洗組成物接觸;(C)用一適當沖洗溶劑沖洗該半導體基材;及(D)選擇地,藉由移除該沖洗溶劑且不會破壞該半導體基材之完整性的任何方式乾燥該半導體基材。
在某些實施例中,該清洗方法更包括由藉由上述方法獲得之該半導體基材形成一半導體裝置(例如,如一半導體晶片之一積體電路裝置)。
在這方法中欲清洗之半導體基材可包含有機及有機金屬殘留物,及另外地包含必須移除之各種金屬氧化物。半導體基材通常由矽、矽鍺、如GaAs之III-V族化合物、或其任一組合構成。該等半導體基材可另外包含如互連形貌體(例如,金屬線及介電材料)之暴露積體電路基材。用於互連形貌體之金屬及金屬合金包括,但不限於:鋁、鋁銅合金、銅、鈦、鉭、鈷、矽、氮化鈦、氮化鉭、鎢及其合金。該半導體基材亦可包含多層層間介電體、氧化矽、氮化矽、碳化矽、氧化鈦及碳摻雜氧化矽。
藉由如將一清洗組成物放入一槽中且將該等半導體基材浸泡及/或浸沒在該清洗組成物中、將該清洗組成物噴灑在該半導體基材上、使該清洗組成物在該半導體基材上流動或其任何組合的任何適當方法,該半導體基材可與該清洗組成物接觸。較佳的是將該半導體基材浸泡在該清洗組成物中。
本揭示之清洗組成物可有效地使用到一大約90℃(例如,大約25℃至大約80℃、大約30℃至大約60℃或40℃至大約60℃)之一溫度。
類似地,清洗時間可依據使用之特定清洗方法及溫度在一大範圍內變化。當在一浸泡批式程序中清洗時,一適當時間範圍係,例如,到達大約60分鐘(例如,
大約1分鐘至大約60分鐘、大約3分鐘至大約20分鐘或大約4分鐘至大約15分鐘)。
一單一晶圓程序之清洗時間範圍可為大約10秒至大約10分鐘(例如,大約15秒至大約9分鐘、大約15秒至大約5分鐘或大約20秒至大約2分鐘)。
為進一步增加本揭示之清洗組成物的清洗力,可使用機械攪拌方式。適當攪拌方式之例子包括使該清洗組成物在該基材上循環、使該清洗組成物流過或噴灑在該基材上及在該清洗程序中進行超音波或超音波震盪攪拌。該半導體基材相對地面之方位可為任何角度。較佳的是水平或垂直方位。
本揭示之清洗組成物可在所屬技術領域中具有通常知識者習知之習知清洗工具中使用。本揭示之組成物的一明顯優點是它們完全地或部份地包括比較不具毒性、不具腐蝕性及不具反應性之成分,藉此該等組成物在大範圍之溫度及處理時間中是穩定的。本揭示之組成物可實際上與用以構成用於批式及單一晶圓清洗之現有及建議半導體晶圓清洗程序的全部材料化學地相容。
該清洗後,該半導體基材可在有或沒有攪拌裝置之情形下用一沖洗溶劑沖洗大約5秒至大約5分鐘。適當沖洗溶劑之例子包括,但不限於:去離子(DI)水、甲醇、乙醇、異丙醇、N-甲基吡咯啶酮、γ-丁內酯、二甲亞碸、乳酸乙酯及丙二醇一甲基醚乙酸酯。或者,可使用具有pH>8之沖洗水溶液(例如稀釋氫氧化銨水溶液)。沖洗
溶劑之較佳例子包括,但不限於:稀釋氫氧化銨水溶液、DI水、甲醇、乙醇及異丙醇。該溶劑可使用類似於使用於施加在此所述清洗組成物者的裝置來施加。該清洗組成物可在開始該沖洗步驟前已由該半導體基材移除或它可在開始該沖洗步驟時仍與該半導體基材接觸。較佳地,在該沖洗步驟中使用之溫度在16℃與27℃之間。
選擇地,在該沖洗步驟後乾燥該半導體基材。可使用所屬技術領域中習知之任何適當乾燥方式。適當乾燥方式之例子包括離心乾燥、使一乾燥氣體流過該半導體基材、用如一熱板或紅外線燈之一加熱裝置加熱該半導體基材、表面張力乾燥(Marangoni drying)、旋轉乾燥(Rotagoni drying)、IPA乾燥或其任何組合。乾燥時間取決於使用之特定方法,但通常為30秒到數分鐘之等級。
在某些實施例中,製造使用在此所述清洗組成物之一積體裝置的一方法可包括以下步驟。首先,將一層光阻施加在一半導體基材上。如此獲得之半導體基材可接著進行一圖案轉印程序,例如一蝕刻或植入程序,以形成一積體電路。接著可藉由一乾或濕剝除方法(例如,一以氧為主之電漿灰化程序)移除該光阻全體。接著可使用在此所述之清洗組成物以上述方式移除在該半導體基材上之剩餘殘留物。接著可處理該半導體基材以便在該基材上形成一或多數另外之電路或可處理以便藉由,例如,組裝(例如,切割及接合)及封裝(例如,晶片密封)形成一半導體晶片。
在此所述之所有文獻(例如,專利、專利申請案公報及文章)的內容因此全部加入作為參考。
參照以下例子更詳細地說明本揭示,該等例子係用以說明且不應被視為限制本揭示之範圍。除非另外指明,否則任何列舉之百分比均為重量百分比(wt%)。除非另外註明,在測試時控制之攪拌係用300rpm之1英吋攪拌棒來進行。
一般程序1
調配物混合
本揭示之清洗組成物係藉由混合,同時攪拌,該等有機溶劑及特純去離子水(DIW)來製備。在獲得一均勻溶液後,添加剩餘成分。使用之全部成分可由市面購得且具有高純度。
一般程序2
用燒杯測試評估清洗
使用已光刻地圖案化,在一電漿金屬蝕刻劑中蝕刻且接著進行氧電漿灰化以便完全移除光阻頂層之光阻/TiOx/SiN/Co/ILD(ILD=層間介電體)或光阻/TiOx/SiN/W/ILD的一多層基材,由一基材清洗PER(後蝕刻殘留物)。
使用4”長塑膠鎖鉗固持測試試片,藉此該試片可接著懸吊在含有大約200毫升本揭示之清洗組成物的一500ml容積玻璃燒杯中。在將該試片浸泡在該清洗組成
物中前,將該組成物預熱至所需測試條件溫度(通常是如上所述之40℃或60℃)同時進行控制之攪拌。接著藉由將被該等塑膠鉗固持之試片放入該被加熱組成物中使得該試片之含PER層側面向該攪拌棒來進行該等清洗測試。該試片在該清洗組成物中保持不動一段時間(通常是2至5分鐘),同時該組成物在控制攪拌下保持在該測試溫度。當到達所需清洗時間時,由該清洗組成物快速地取出該試片且放入裝有一室溫(~17℃)之400ml DI水的一500ml塑膠燒杯並緩慢攪拌。將該試片留在該DI水之燒杯中大約30秒,接著快速地取出並在一DI水流下在室溫下沖洗大約30秒。將該試片立即暴露於來自一手持式吹氮槍之一氮氣流,使在該試片表面上之所有液滴被吹離該試片,且進一步完全地乾燥該試片裝置表面。在這最後氮乾燥步驟後,由該塑膠鉗固持器移除該試片且放入一有蓋塑膠載體中並且該裝置側向上以便進行不超過大約2小時之短期儲存。接著收集掃描式電子顯微鏡(SEM)影像以取得在該已清洗測試試片裝置表面上之重要形貌體。
一般程序3
用燒杯測試評估材料相容性
將Co覆蓋之矽基材、覆蓋W之矽基材、TiOx在SiO2上覆蓋之矽基材、SiN覆蓋之矽基材、ILD覆蓋之矽基材、SiC覆蓋之矽基材及W合金覆蓋之矽基材切成大約1英吋×1英吋正方形測試試片以便進行材料相容性測試。使用一Woollam M-2000X藉由用於金屬膜(Co、W)
之4點探針、CDE Resmap 273,或藉由用於介電膜(TiOx、SiN、SiC及ILD)的橢偏儀開始測量該等測試試片之厚度或表面電阻。接著將該等測試試片安裝在該等4”長塑膠鎖鉗上且在該試片之含Co、W、W合金、TiOx、SiN、SiC或ILD側面向該攪拌棒之情形下如在一般程序2中之清洗程序中所述地處理10分鐘。
在最後氮乾燥步驟後,由該塑膠鉗固持器移除該試片且放入一有蓋塑膠載體中。接著使用一Woollam M-2000X藉由用於金屬膜(Co、W及W合金)之4點探針、CDE Resmap 273或藉由用於介電膜(TiOx、SiN、SiC及ILD)的橢偏儀在該後處理測試試片表面上收集該後厚度或表面電阻。
調配物例FE-1至FE-3
表1包括由一般程序1製備之調配物FE-1至FE-3(包括一含硫添加劑)。在表1至6中,「DEGBE」表示二乙二醇丁醚;「Hex glycol」表示己二醇;「MSA」表示甲磺酸;且「DTPA」表示二伸乙三胺五乙酸。
例1至3
清洗劑與暴露金屬或介電體之相容性
在65℃依據一般程序2測試調配物FE-1、FE-2及FE-3之清洗力及依據一般程序3測試材料相容性4分鐘。測試各調配物之多數樣本。該等結果顯示這些調配物充分地移除後蝕刻/灰化殘留物。該等清洗組成物對TiOx、W合金、Co、SiN、ILD、W、Al2O3、SiC及四原矽酸乙酯(TEOS)的蝕刻速度(ER)(埃/分鐘)顯示在表2中。
表2中之數據顯示這揭示之調配物(即,FE-1、FE-2及FE-3)未明顯地蝕刻通常在半導體裝置中存在之不希望移除的半導體材料(例如TiOx、Co、W、SiN、ILD、Al2O3、SiC及TEOS)。此外,似乎在FE-2中使用之環丁碸有助於減少Co蝕刻速度。
調配物例FE-4至FE-11及CFE-1至CFE-4
表3包括由一般程序1製備之調配物例FE-4至FE-11及比較調配物CFE-1至CFE-4。
例4至11及比較例1至4
清洗劑與暴露金屬之相容性
在65℃依據一般程序2測試調配物FE-4及比較調配物
CFE-1至CFE-4之清洗力及依據一般程序3測試材料相容性4分鐘。該等清洗組成物對TiOx、W合金及Co的蝕刻速度(ER)(埃/分鐘)顯示在表4中。
在表4中之數據顯示沒有一含硼化合物之比較調配物(即,CFE-1至CFE-4)大致具有對Co比較高之蝕刻速度。相反地,包含一含硼化合物之這揭示的清洗調配物(即,FE-4至FE-11)具有一意外地低之Co蝕刻速度。因此,這揭示之清洗調配物可用於清洗後蝕刻/灰化殘留物且不會明顯地蝕刻在半導體裝置中存在之不希望移除的暴露Co。
調配物例FE12-至FE-13及CFE-5至CFE-6
表5包括由一般程序1製備之調配物FE-12至
FE-13及比較調配物CFE-5至CFE-6。
例12至13及比較例5至6
清洗劑與暴露金屬之相容性
在65℃依據一般程序2測試調配物FE-12至FE-13及比較調配物CFE-5至CFE-6之清洗力及依據一般程序3測試材料相容性4分鐘。該等清洗組成物對TiOx、W合金及Co的蝕刻速度(ER)(埃/分鐘)顯示在表6中。
在表6中之數據顯示沒有一含硼化合物之比較調配物(即,CFE-5至CFE-6)大致具有對Co比較高之蝕刻速度。相反地,包含一含硼化合物之這揭示的清洗調配物(即,FE-12至FE-13)具有一意外地低之Co蝕刻速度。因此,這揭示之清洗調配物可用於清洗後蝕刻/灰化殘留物且不會明顯地蝕刻在半導體裝置中存在之不希望移除的暴露Co。
雖然本揭示已參照其某些實施例詳細說明過了,但應了解的是多數修改例及變化例在所述及所請求之精神及範疇內。
Claims (21)
- 如請求項1之組成物,其中該組成物具有7至11之一pH。
- 如請求項1之組成物,其中該羥胺係該組成物重量之5%至10%。
- 如請求項1之組成物,其中該組成物包含二有機溶劑。
- 如請求項4之組成物,其中該等二有機溶劑各獨立地選自於由烷二醇、烷二醇醚及碸構成之群組。
- 如請求項5之組成物,其中該等二有機溶劑各獨立地選自於由己二醇、二乙二醇丁醚及環丁碸構成之群組。
- 如請求項1之組成物,其中該至少一有機溶劑係該組成物重量之65%至95%。
- 如請求項1之組成物,更包含至少一有機 酸。
- 如請求項8之組成物,其中該至少一有機酸包含一羧酸或一磺酸。
- 如請求項9之組成物,其中該至少一有機酸包含甲磺酸。
- 如請求項8之組成物,其中該至少一有機酸係該組成物重量之0.01%至0.5%。
- 如請求項1之組成物,其中該至少一含硼化合物包含硼酸。
- 如請求項13之組成物,其中R係苯基。
- 如請求項1之組成物,其中該含硼化合物係該組成物重量之0.002%至0.2%。
- 如請求項1之組成物,其中該水係該組成物之5%至28%。
- 一種清洗方法,其包含以下步驟:使包含後蝕刻殘留物或後灰化殘留物之一半導體基材與如請求項1至16中任一項之清洗組成物接觸。
- 如請求項17之方法,其中該半導體基材更包含一層,該層包含選自於由Cu、Co、W、AlOx、AlN、AlOxNy、Ti、TiN、Ta、TaN、TiOx、ZrOx、HfOx及 TaOx構成之群組的一材料。
- 如請求項17之方法,更包含在該接觸步驟後用一沖洗溶劑沖洗該半導體基材之步驟。
- 如請求項19之方法,更包含在該沖洗步驟後乾燥該半導體基材之步驟。
- 如請求項17之方法,更包含由該半導體基材形成一半導體裝置之步驟。
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