TWI617705B - 銅腐蝕抑制系統 - Google Patents
銅腐蝕抑制系統 Download PDFInfo
- Publication number
- TWI617705B TWI617705B TW104122412A TW104122412A TWI617705B TW I617705 B TWI617705 B TW I617705B TW 104122412 A TW104122412 A TW 104122412A TW 104122412 A TW104122412 A TW 104122412A TW I617705 B TWI617705 B TW I617705B
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- Taiwan
- Prior art keywords
- acid
- aromatic moiety
- group
- polyfunctional
- composition
- Prior art date
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- 238000005260 corrosion Methods 0.000 title claims abstract description 65
- 230000007797 corrosion Effects 0.000 title claims abstract description 65
- 239000010949 copper Substances 0.000 title claims abstract description 37
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 20
- 230000005764 inhibitory process Effects 0.000 title claims description 12
- 239000000203 mixture Substances 0.000 claims abstract description 143
- 239000002253 acid Substances 0.000 claims abstract description 75
- 229910052751 metal Inorganic materials 0.000 claims abstract description 72
- 239000002184 metal Substances 0.000 claims abstract description 72
- 238000004140 cleaning Methods 0.000 claims abstract description 68
- 150000001412 amines Chemical class 0.000 claims abstract description 58
- 230000002401 inhibitory effect Effects 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 21
- 125000003277 amino group Chemical group 0.000 claims abstract description 17
- 239000000126 substance Substances 0.000 claims abstract description 14
- 238000005498 polishing Methods 0.000 claims abstract description 12
- 239000010936 titanium Substances 0.000 claims abstract description 11
- 238000004380 ashing Methods 0.000 claims abstract description 10
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 6
- 239000010941 cobalt Substances 0.000 claims abstract description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 6
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 6
- 239000010937 tungsten Substances 0.000 claims abstract description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000001020 plasma etching Methods 0.000 claims abstract description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 54
- 125000003118 aryl group Chemical group 0.000 claims description 52
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- 239000004065 semiconductor Substances 0.000 claims description 31
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 30
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 30
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 20
- 150000007942 carboxylates Chemical class 0.000 claims description 18
- 239000003960 organic solvent Substances 0.000 claims description 18
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 17
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 claims description 17
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 16
- 239000003112 inhibitor Substances 0.000 claims description 16
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 15
- 150000000000 tetracarboxylic acids Chemical class 0.000 claims description 15
- 150000003628 tricarboxylic acids Chemical class 0.000 claims description 15
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 13
- 229920000768 polyamine Polymers 0.000 claims description 13
- 229920002873 Polyethylenimine Polymers 0.000 claims description 12
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 10
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 9
- -1 glycol ethers Chemical class 0.000 claims description 9
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 claims description 9
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 8
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 8
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 7
- 150000007513 acids Chemical class 0.000 claims description 7
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 7
- 239000001630 malic acid Substances 0.000 claims description 7
- 235000011090 malic acid Nutrition 0.000 claims description 7
- MOVBJUGHBJJKOW-UHFFFAOYSA-N methyl 2-amino-5-methoxybenzoate Chemical compound COC(=O)C1=CC(OC)=CC=C1N MOVBJUGHBJJKOW-UHFFFAOYSA-N 0.000 claims description 7
- 239000000872 buffer Substances 0.000 claims description 6
- 229940113088 dimethylacetamide Drugs 0.000 claims description 6
- 239000003381 stabilizer Substances 0.000 claims description 6
- DIIIISSCIXVANO-UHFFFAOYSA-N 1,2-Dimethylhydrazine Chemical compound CNNC DIIIISSCIXVANO-UHFFFAOYSA-N 0.000 claims description 5
- HQFQTTNMBUPQAY-UHFFFAOYSA-N cyclobutylhydrazine Chemical compound NNC1CCC1 HQFQTTNMBUPQAY-UHFFFAOYSA-N 0.000 claims description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 5
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 5
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 5
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 5
- 150000007519 polyprotic acids Polymers 0.000 claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 5
- 229910017855 NH 4 F Inorganic materials 0.000 claims description 4
- KVBCYCWRDBDGBG-UHFFFAOYSA-N azane;dihydrofluoride Chemical compound [NH4+].F.[F-] KVBCYCWRDBDGBG-UHFFFAOYSA-N 0.000 claims description 4
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- NHWGPUVJQFTOQX-UHFFFAOYSA-N ethyl-[2-[2-[ethyl(dimethyl)azaniumyl]ethyl-methylamino]ethyl]-dimethylazanium Chemical compound CC[N+](C)(C)CCN(C)CC[N+](C)(C)CC NHWGPUVJQFTOQX-UHFFFAOYSA-N 0.000 claims 3
- 239000013543 active substance Substances 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 2
- 239000002002 slurry Substances 0.000 abstract description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 18
- 235000012431 wafers Nutrition 0.000 description 17
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- 239000000758 substrate Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- 238000004377 microelectronic Methods 0.000 description 7
- 239000002738 chelating agent Substances 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 238000009472 formulation Methods 0.000 description 5
- 229920002125 Sokalan® Polymers 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 238000011109 contamination Methods 0.000 description 4
- 229920002120 photoresistant polymer Polymers 0.000 description 4
- 239000004584 polyacrylic acid Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 229910001111 Fine metal Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000000010 aprotic solvent Substances 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- UPCIBFUJJLCOQG-UHFFFAOYSA-L ethyl-[2-[2-[ethyl(dimethyl)azaniumyl]ethyl-methylamino]ethyl]-dimethylazanium;dibromide Chemical compound [Br-].[Br-].CC[N+](C)(C)CCN(C)CC[N+](C)(C)CC UPCIBFUJJLCOQG-UHFFFAOYSA-L 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 238000001465 metallisation Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- RWXZXCZBMQPOBF-UHFFFAOYSA-N 5-methyl-1H-benzimidazole Chemical compound CC1=CC=C2N=CNC2=C1 RWXZXCZBMQPOBF-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- QLZHNIAADXEJJP-UHFFFAOYSA-L dioxido-oxo-phenyl-$l^{5}-phosphane Chemical compound [O-]P([O-])(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-L 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 150000002222 fluorine compounds 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
- 229910052736 halogen Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229940042055 systemic antimycotics triazole derivative Drugs 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 125000005590 trimellitic acid group Chemical group 0.000 description 1
- 239000011345 viscous material Substances 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
- C11D3/30—Amines; Substituted amines ; Quaternized amines
-
- 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0073—Anticorrosion compositions
-
- 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
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2082—Polycarboxylic acids-salts thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2086—Hydroxy 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
- C11D3/26—Organic compounds containing nitrogen
- C11D3/33—Amino carboxylic 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
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3723—Polyamines or polyalkyleneimines
-
- 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
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
-
- 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
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
- C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions
-
- C—CHEMISTRY; METALLURGY
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Abstract
本發明提供用於銅(Cu)、鎢(W)、鈦(Ti)、鉭(Ta)、鈷(Co)及鋁(Al)的金屬腐蝕抑制清潔組合物、方法及系統。該等金屬腐蝕抑制清潔組合物藉由使用二化學藥品的組合-具有多於一胺基的至少一多官能基胺及具有多於一羧酸根的至少一多官能基酸-來提供腐蝕抑制效應。該等金屬腐蝕抑制清潔組合物能有效清潔高密度電漿蝕刻繼而以含氧電漿灰化所衍生的殘餘物;及化學機械拋光(CMP)之後剩下的漿料粒子和殘餘物。
Description
本專利案係2014年7月14日申請的美國臨時專利案序號第62/024,046號的非臨時案,在此以引用的方式將其全文併入本文。
本發明關於金屬腐蝕抑制劑、金屬腐蝕抑制清潔組合物及使用該等金屬腐蝕抑制劑的金屬腐蝕抑制清潔系統和方法。本發明關於適用於含精細金屬例如銅(Cu)、鎢(W)、鈦(Ti)、鉭(Ta)、鈷(Co)和鋁(Al),明確地說銅互連結構,的半導體裝置之應用。
由於微電子裝配積體度提高而且圖案化微電子裝置尺寸降低,使此技藝變得逐漸通通運用銅金屬化層、低-k和高-k介電層。
在該製程中,將光阻劑薄膜沉積於晶圓基材上,而且接著在該薄膜上造電路設計的影像。在烘烤之後,利用光阻劑顯影劑移除未聚合的阻劑。接著藉由反應性電
漿蝕刻氣體或化學蝕刻劑溶液的方式將結果產生的影像轉移至底下的材料,其一般為介電質或金屬。該等蝕刻劑氣體或化學蝕刻劑溶液選擇性地攻擊該基材的未經光阻劑保護的區域。由於該電漿蝕刻程序的結果,使光阻劑、蝕刻氣體和經蝕刻的材料的副產物以殘餘物方式沉積於該晶圓或基材的蝕刻開口側壁周圍或上面。
接在該電漿蝕刻及/或灰化程序之後的這些蝕刻劑及/或灰化殘餘物的移除據證實有問題。無法完全移除或中和這些殘餘物會造成水氣吸收和會造成金屬結構腐蝕的不欲材料的形成。電路材料被該等不欲的材料腐蝕而且產生電路配線斷絕和非所欲的電阻提高。
再者,在利用化學機械拋光(CMP)形成金屬配線時,晶圓的表面和背部明顯被金屬拋光之後留下的拋光劑、拋光所產生的拋光碎片及該拋光劑和拋光墊所含的金屬雜質污染,因此經過拋光步驟必然得清潔其表面。
一般,為了移除存於晶圓表面上的粒子,吾人所欲為以鹼溶液進行清潔,因為阻止粒子移離其表面之後再黏附很重要。
然而,為了有效地移除金屬離質,吾人所欲為以具有強力金屬溶解力的酸溶液進行清潔。然而,誠如所知,金屬會受到這些鹼溶液和酸溶液腐蝕。因此,在以這些溶液清潔裸露出金屬配線層的晶圓表面之案例中,通常會有清潔之後該金屬表面受到腐蝕,藉以造成配線阻抗提高且再者該配線損壞的問題。
於是有人試圖使用腐蝕抑制劑來避免金屬腐蝕。
不同的先前技藝組合物皆有缺點,包括不欲地移除金屬或絕緣層及腐蝕期望的金屬層,特別是銅或銅合金特徵。有些先前技藝配方運用腐蝕抑制添加物防止在該清潔程序期間不欲的銅金屬腐蝕。然而,那些習用的腐蝕抑制添加物對該清潔程序通常有不利用的效應,因為那些添加物會與殘餘物交互作用而且抑制此殘餘物溶入該清潔流體中。
舉例來說,鈍化劑化學藥品,例如芳香族烴化合物,舉例來說,苯并三唑及5-甲基苯并咪唑,在完成該清潔程序之後不會輕易沖洗掉該銅表面。這樣的添加物因此留在試著要清潔的表面上,而且造成積體電路的污染。該等積體電路的污染會使污染區域的電阻不利地提高而且造成該電路內不可預測的導電失敗。
據知其他抗氧化劑(犧牲)化學藥品,例如苯磷二酚等等有浴壽命的問題。
已經有人做了更多研究並且彙總如下。
US 6,755,989描述一種半導體晶圓清潔配方,其包括1至21重量%氟化物來源、20至55重量%有機胺(類)、0.5至40重量%含氮組分,例如,含氮羧酸或亞胺、23至50重量%水及0至21重量%金屬螯合劑(類)。該等配方可用以在阻劑電漿灰化步驟之後繼而從晶圓移除殘餘物,例如從含精細銅互連結構的半導體晶圓移除無機殘餘
物。
US 6,224,785描述用於清潔半導體基材上的無機殘餘物之氟化銨水溶液及含胺組合物。用於後電漿灰化半導體裝配的半導體晶圓清潔配方以所示的重量範圍百分比包含下列組分:氯化銨及/或其衍生物:1至21重量%;有機胺或二胺的混合物:20至55重量%;水:23至50重量%;金屬螯合劑或螯合劑的混合物:0至21重量%。
US 7,521,406描述用於清潔微電子基材的微電子清潔組合物,而且特別是可配合微電子基材以及Al或Al(Cu)金屬化的基材使用且與其具有改良的相容性之清潔組合物,該等微電子基材的特徵為二氧化矽、敏感性低-k或高-k介電質及銅、鎢、鉭、鎳、金、鈷、鈀、鉑、鉻、釕、銠、銥、鉿、鈦、鉬、錫及其他金屬化層,而且先進的互連件技術係由包含鹵酸類、鹽類和其衍生物的微電子清潔組合物提供。
因此本發明之一目的在於提供用於保護該半導體晶圓或基材上的銅結構的腐蝕抑制劑。
本發明之另一目的在於提供在該殘餘物移除程序之後易於藉由水或其他沖洗介質沖洗該基材,藉以降低該積體電路的污染之腐蝕抑制劑。
本發明之另一目的在於提供在阻劑灰化步驟及/或CMP步驟之後繼而有效地移除殘餘物而不會攻擊及/或有可能使欲留在該晶圓上的精細金屬結構劣化的化學配方(或組合物)及系統。
本發明之另一目的在於提供在阻劑灰化步驟及/或CMP步驟之後繼而有效地移除殘餘物之使用該等腐蝕抑制劑的方法、化學藥品組合物及系統。
藉由使用所揭示的金屬腐蝕抑制組合物、方法和系統來滿足這些需求。
於一態樣中,提供一種金屬腐蝕抑制清潔組合物。該組合物包含:1)0.1重量%至5重量%的至少一多官能基酸;2)0.0至30重量%的至少一多官能基胺;3)剩下部分實質上為液體載劑;其中該多官能基胺係一分子中具有多於一胺基的胺或聚胺;該多官能基酸係一分子中具有多於一羧酸根的酸或多元酸;及該液體載劑係選自由有機溶劑、水及其組合所組成的群組。
於另一態樣中,提供一種從含至少一金屬的半導體晶圓有效地移除殘餘物之方法,該方法包含以下步驟:a)提供至少一表面含有至少一金屬和殘餘物的半導體晶圓;b)提供金屬腐蝕抑制清潔組合物,其包含:(i)0.1重量%至5重量%的至少一多官能基酸;(ii)0.0至30重量%的至少一多官能基胺;及
(iii)剩下部分實質上為液體載劑;其中該多官能基胺係一分子中具有多於一胺基的胺或聚胺;該多官能基酸係一分子中具有多於一羧酸根的酸或多元酸;及該液體載劑係選自由有機溶劑、水及其組合所組成的群組;c)使該半導體晶圓與該金屬腐蝕抑制清潔組合物接觸;及d)清潔該等殘餘物;其中使具有殘餘物的至少一部分表面與該金屬腐蝕抑制組合物接觸。
於又另一態樣中,提供一種半導體晶圓清潔系統。該系統包含:一半導體晶圓,其至少一表面含有至少一金屬和殘餘物;及一金屬腐蝕抑制清潔組合物,其包含:(i)0.1重量%至5重量%的至少一多官能基酸;(ii)0.0至30重量%的至少一多官能基胺;及(iii)剩下部分實質上為液體載劑;其中該多官能基胺係一分子中具有多於一胺基的胺或聚胺;
該多官能基酸係一分子中具有多於一羧酸根的酸或多元酸;及該液體載劑係選自由有機溶劑、水及其組合所組成的群組;其中使具有殘餘物的至少一部分表面與該金屬腐蝕抑制組合物接觸。
該多官能基胺包括,但不限於聚乙烯亞胺、三胺、五胺、六胺及其組合。
該多官能基酸包括,但不限於二羧酸(例如丙二酸、蘋果酸等等)、具有芳香族部分的二羧酸(例如苯二甲酸等等)及其組合;三羧酸(例如檸檬酸等等)、具有芳香族部分的三羧酸(例如偏苯三甲酸等等)及其組合;四羧酸(例如乙二胺四醋酸(EDTA)等等)、具有芳香族部分的四羧酸(例如苯均四酸)及其組合。
該有機溶劑佔至高70重量%;而且包括,但不限於丙二醇(PG)、二醇醚類、非質子性溶劑類例如N-甲基吡咯烷酮(NMP)、二甲基亞碸(DMSO)、二甲基乙醯胺(DMAC)、環丁碸、二甲基甲醯胺(DMF)及其組合。
該金屬腐蝕抑制清潔組合物能另外包含氟化物來源、鹼及任意地金屬螯合劑、表面活性劑、安定劑、腐蝕抑制劑及緩衝劑。
該氟化物來源佔0.01重量%至1.0重量%;而且包括,但不限於氫氟酸(HF)、氟化銨(NH4F)、二氟化銨(NH4HF2)、氟化四甲基銨(TMAF)及其組合。
該鹼佔至高50重量%;而且包括,但不限於三乙醇胺(TEA)及經取代的衍生物、二乙醇胺及經取代的衍生物、單乙醇胺及經取代的衍生物及其組合。
該金屬腐蝕抑制清潔組合物的pH介於5至10。
本發明的其他態樣、特徵和具體實施例從隨後的揭示內容及附加的申請專利範圍來看將更完全顯而易見。
本發明提供供銅(Cu)、鎢(W)、鈦(Ti)、鉭(Ta)、鈷(Co)和鋁(Al)用的新金屬腐蝕抑制劑。本發明另外提供含有清潔組合物或適用於清潔表面含有精細金屬結構的半導體基材/晶圓的組合物(彼等可交換地使用)之新穎金屬腐蝕抑制劑。該等組合物能有效清潔高密度電漿蝕刻繼而以含氧電漿灰化所衍生的殘餘物;及CMP(化學機械拋光)之後留下來的漿料粒子和殘餘物
本發明有利地使用二化學藥品的組合:至少一多官能基胺;及至少一多官能基酸。
該多官能基胺係具有多於一胺基的胺或聚胺。該多官能基酸係具有多於一羧酸根的酸或多元酸。
不欲為理論所束縛,咸相信該多官能基胺(一分子中具有多重胺基)及多官能基酸(一分子中具有多於一羧酸根)形成能保持錯合狀態的錯合物。該錯合物提供明確地說被吸引到游離金屬原子且因此透過羧酸根部分(該等羧
酸根係橋接於胺類和金屬例如Cu表面之間)接附於金屬表面而形成保護層以在該清潔程序的期間保護被清潔組合物腐蝕的金屬表面之官能基。因此,金屬例如表面的鈍化係透過阻斷金屬與大氣氧的接觸而引起金屬氧化物金屬氧化物形成的抑制。
再者,該等新穎金屬腐蝕抑制組合物能藉由去離子水或其他溶液輕易地沖洗掉而且因此在該清潔操作之後留下非常少的污染在該銅表面上。
該等組合物的益處之一係長的浴壽命,因為此聚胺-多元酸錯合物不被視為抗氧化劑。此錯合物仍舊運用以下使用鈍化劑來保護Cu以免腐蝕的原理:其吸附能比廣為採納的Cu腐蝕抑制劑,像是苯并三唑或其他三唑衍生物,的吸附能更低許多。
更明確地說,該等金屬腐蝕抑制清潔組合物含有(i)具有多於一胺基的至少一胺或聚胺;(ii)具有多於一羧酸根的至少一酸或多元酸;及(iii)剩下部分實質上為液體載劑,其包括,但不限於有機溶劑、水及其組合。
該等金屬腐蝕抑制清潔組合物能另外含有(iv)氟化物來源,及(v)鹼。
任意地,該等組合物可含有金屬螯合劑、表面活性劑、安定劑、腐蝕抑制劑及緩衝劑中的一或多者。
該多官能基胺(具有多於一胺基的胺或聚胺)包括,但不限於,聚乙烯亞胺、三胺、五胺及六胺。
該等組合物適當地含有0.0重量%至30重量%
的多官能基胺;較佳地0.1重量%至25重量%,而且更佳地0.5重量%至20重量%具有多於一胺基的胺或聚胺。
該多官能基酸係具有多於一羧酸根的酸或多元酸包括,但不限於(i)二羧酸根酸(例如丙二酸、蘋果酸等等);具有芳香族部分的二羧酸(例如苯二甲酸等等)及其組合;(ii)三羧酸(例如檸檬酸等等)、具有芳香族部分的三羧酸(例如偏苯三甲酸等等)及其組合;及(iii)四羧酸(例如乙二胺四醋酸(EDTA)等等);具有芳香族部分的四羧酸(例如苯均四酸)及其組合。
該等組合物適當地含有0.1重量%至5重量%的多官能基酸;較佳地0.25重量%至3重量%,而且更佳地0.5重量%至2.0重量%具有多於一羧酸根的酸或多元酸。
該氟化物來源包括,但不限於氫氟酸(HF)、氟化銨(NH4F)、二氟化銨(NH4HF2)、氟化四甲基銨(TMAF)。
該等組合物適當地含有0.01重量%至1.0重量%氟化物來源,較佳地0.1重量%至1.0重量%,而且更佳地0.5重量%至1.0重量%氟化物來源。
該有機溶劑包括,但不限於丙二醇(PG)、二醇醚類、非質子性溶劑類例如N-甲基吡咯烷酮(NMP)、二甲基亞碸(DMSO)、二甲基乙醯胺(DMAC)、環丁碸及二甲基甲醯胺(DMF)。
該等組合物適當地含有至高70重量%有機溶劑;較佳地至高60重量%,而且更佳地至高50重量%有機溶劑。
該等組合物適當地含有至高30重量%水,較佳地至高25重量%,而且更佳地至高22重量%水。
該等組合物適當地含有其他胺類當鹼以有效地移除殘餘物。該胺類能包括,但不限於三乙醇胺(TEA)、二乙醇胺、單乙醇胺及其經取代的衍生物。
該等組合物適當地含有至高50重量%鹼;較佳地至高40重量%,而且更佳地至高30重量%鹼。
由於可用於或欲用於本發明組合物的指定終端用途應用,使該等組合物可含有一或更多金屬螯合劑、表面活性劑、安定劑、腐蝕抑制劑、緩衝劑及共溶劑。
附帶地,本發明的組合物的pH介於5至10;較佳地6至9,而且更佳地7.5至8.5。
本發明的特徵和優點係藉由下列非限定實施例更完全地加以顯示。在下示的實施例中,除非另行指明,否則所有百分比皆為重量百分比。該等組合物的pH係大約7.5至8.5。
工作組合物45包含49.34重量% PG、4.13重量%檸檬酸(於水中的濃度29%)、28.55重量% TEA、16.98重量% HF(於水中的濃度5%)及1.00重量%聚乙烯亞胺(mw=800)。
比較組合物45A、45D和45G的化學組成係顯示於表I。
組合物45A係以醋酸(具有一羧酸根)代替檸檬酸(具有三羧酸根)而製備。因此,組合物45A沒有多官能基酸。
組合物45C係以單乙醇胺(MEA)(非多官能基胺)代替聚乙烯亞胺(mw=800)(多官能基胺)而製備。因此,組合物45C沒有多官能基胺。除此之外,檸檬酸係由聚丙烯酸(脂肪族多鹽基酸)(於水中的濃度35%)來代替。
組合物45D係以去離子水代替部分(23.95重量%)丙二醇而製備。因此,組合物45D係為45之含水更多的組合物。
請注意45A、45C和45G中有另外的小量去離子水應不得影響Cu ER的效能,因為該等組合物會有來自,舉例來說,檸檬酸(於水中的濃度29%)、HF(於水中的濃度5%)及聚丙烯酸(於水中的濃度35%)的水。
組合物45G沒使用聚乙烯亞胺(mw=800)製備。因此,組合物45G沒有多官能基胺。
組合物47N係45G之含水更多的組合物。該組合物沒有多官能基胺而且部分丙二醇係由去離子水來代替。
此組組合物係於空白銅基材上測試。將於0至5,15至30,and 15至60分鐘下測的銅蝕刻速率(ER)顯示於
表I。
工作組合物45提供給銅最佳的腐蝕抑制作用。該銅蝕刻速率小於2.09埃/分鐘。
不含該新穎腐蝕抑制系統的比較組合物得到下列蝕刻速率:不含多官能基酸的45A得到6.74至10.87埃/分鐘的Cu ER;不含多官能基胺的45C得到8.32至10.07埃/分鐘的Cu ER;及不含多官能基胺的45G係為7.55至7.70埃/分鐘;及不含多官能基胺之含水更多的47N係為7.20至10.80埃/分鐘。
兼具多官能基胺和多官能基酸,但是還另外加去離子水的45D的Cu蝕刻速率有提升一些,但是仍舊得到3.7埃/分鐘的低蝕刻速率。
此組工作實施例顯示含有具有多於一胺基的多官能基胺和具有多於一羧酸根(舉例來說,3羧酸根)的多官能基酸之腐蝕抑制劑組合的組合物得到意外且獨特的協同腐蝕抑制效應。
進行此組實驗係為了測試包含檸檬酸和具有芳香族部分的另一多官能基酸之組合物。具有芳香族部分的多官能基酸係偏苯三甲酸、苯均四酸及苯二甲酸。
組合物53J包含46.67重量% PG、4.83重量%檸檬酸(於水中的濃度29%)、28.00重量% TEA、20.00重量% HF(於水中的濃度5%)及1.00重量%聚乙烯亞胺(mw=800)。
組合物53G係藉由以0.20重量%的苯均四酸來代替組合物53J中的小部分檸檬酸而製備。
如表II所示,組合物53J提供0.28至2.46埃/分鐘的Cu蝕刻速率。組合物53G提供0.49至3.19埃/分鐘的Cu蝕刻速率。因此,具有芳香族部分的多官能基酸的添加不會影響該Cu ER。
進行一群組組合物47系列的實驗係為了測試具有芳香族部分的多官能基酸在該等組合物中的用途。被測試之具有芳香族部分的多官能基酸係偏苯三甲酸、苯均四酸及苯二甲酸。
除此之外,如表III所示,此組實驗係以含水更多的組合物來進行。那些組合物能使用較高重量%的水。
該等組合物中使用具有芳香族部分之一多官能基酸來進行一組實驗(組合物47A至47B)。
組合物47A係利用DIW、丙二醇(PG)、三乙醇胺(TEA)、HF(於水中的濃度5%)、2.20重量%偏苯三甲酸(多官能基酸)及聚乙烯亞胺(mw=800)(多官能基胺)來製備。
組合物47B係以非常類似於組合物47A的方式,利用DIW、PG、TEA、HF(於水中的濃度5%)、2.70重量%苯二甲酸(多官能基酸)及聚乙烯亞胺(mw=800)(多官能基胺)來製備。
如表III所示,單獨使用多於2.0重量%量的那些具有芳香族部分的多官能基酸(沒使用檸檬酸)使組合物47A和47B的Cu ER分別地升至6.03至6.52埃/分鐘,及6.75至7.27埃/分鐘。
以含有芳香族部分的多官能基酸來代替不含芳香族部分的多官能基酸無法得到好的Cu ER。
進行另一群組的實驗(組合物47E和47F)係為了使用該組合物中的至少二多官能基酸:檸檬酸與偏苯三甲酸、苯均四酸或苯二甲酸的組合。
以一多官能基酸(7.15重量%檸檬酸(29%))製備的組合物47L係當組合物47E和47F的控制組使用。
組合物47E係利用6.8重量%檸檬酸(29%)和0.10重量%苯均四酸的組合來製備。
組合物47F係利用6.8重量%檸檬酸(29%)和0.10重量%苯二甲酸的組合來製備。
如表III所示,具有芳香族部分的多官能基酸加於該等組合物不會影響Cu蝕刻速率。組合物47C得到2.6至4.0埃/分鐘,組合物47E和47F分別地得到2.6 4.1至埃/分鐘和2.78至3.38埃/分鐘。這些結果與利用含水較少的組合物的實施例2之結果一致。
進行又另一群組的實驗(配方47H、47I和47J)係為了測試使用不同群組的酸類之組合物:組合物47H係利用醋酸(具有一羧酸根,亦即,非多官能基酸)來製備;組合物47I係利用蘋果酸(具有二羧酸根)來製備;而且組合物47J係利用丙二酸(具有二羧酸根)來製備。除此之外,那些組合物也使用苯均四酸(含有芳香族部分的多官能基酸)。單獨使用醋酸製備的組合物47M係當組合物47H的控制組使用。
如表III所示,單獨含有醋酸的組合物47M具有高Cu ER(7.2至9.6埃/分鐘),其與含水較少的組合物45A的結果(6.74至10.87埃/分鐘)(顯示於表I)一致。0.10重量%苯均四酸加於組合物47H稍微地降低但是仍舊得到高Cu ER 7.68至7.77埃/分鐘。
具有多官能基酸類的組合物47I和47J蘋果酸及丙二酸分別地得到3.01至3.62埃/分鐘和2.79至3.38埃/分鐘的較低Cu ER。
此組工作實施例再次顯示該等組合物利用含水較少的組合物得到需要具有多於一胺基的多官能基胺及具有多於一羧酸根的多官能基酸(舉例來說,2或3羧酸根)的組合之最佳腐蝕抑制系統。
此組工作實施例顯示該等組合物能使用較高重量%的水而不會改變Cu相容性。
總之,工作實施例1至3證實具有多於一胺基的多官能基胺和具有多於一羧酸根的多官能基酸組合而成的組合物達成意外且獨特的協同腐蝕抑制效應。
如表4所示,組合物45B係利用聚乙烯亞胺(mw=800);及聚丙烯酸來製備。然而,該二者一旦混合之後,即形成不溶於水或有機溶劑之有黏性的糊狀材料。有人強烈認為該黏性物質係由多元酸與多胺之間的交互作用引起的錯合物。已知多胺與多元酸之間的交互作用能用以使用朗謬-布洛傑(Langmuir-Brodgett)技術來沉積膜層。
與45B相比,組合物47G具有較小量的0.30重量%的聚丙烯酸溶液(於水中的濃度35%)。該組合物47G得到好的Cu相容性(2.42至3.64埃/分鐘的Cu ER)但是該溶液遇到濁度的問題。
從組合物45B和47G出現的結果來看,顯而易見要維持含水介質中的多酸-多胺錯合物需要對的多官能基酸和多官能基胺的組合。為了避免該等問題,最好多官能基酸和多官能基胺中之其一係非聚合性。該等工作實施例顯示適當選擇分子的這些組合能形成澄清溶液。
多官能基酸分子和多官能基胺分子能從以下選擇(1)具有多重胺官能基的聚合物分子和具有多重酸官
能基的小(寡聚合)分子,或(2)具有多重酸官能基的聚合物分子和具有多重胺官能基的小(寡聚合)分子。
該等工作實施例顯示適當選擇分子的這些組合能形成澄清溶液。
進行此組實驗係為了測試表5所示的組合物。106E係利用單乙醇胺(MEA)和檸檬酸來製備。106G/H/C/i/J/K係利用二伸乙基三胺(DETA)和檸檬酸來製備。
該結果證實該等組合物仍舊能提供好的腐蝕抑制效應。
前述實施例和較佳具體實施例的描述理應視為舉例說明,而非限制如申請專利範圍所界定的發明。由於能輕易了解,上述特徵的許多變化和組合皆能利用而不會悖離申請專利範圍所述的發明。這樣的變化不得視為悖離本發明的精神和範疇,而且意欲將所有這樣的變化皆算在下列申請專利範圍的範疇以內。
Claims (23)
- 一種金屬腐蝕抑制的清潔組合物,其由下列組成:1)0.1重量%至5重量%的至少一多官能基酸,以組合物的總重量為基準;2)0.1至25重量%的至少一多官能基胺,以組合物的總重量為基準;3)0.01重量%至5.7重量%的氟化物來源;4)剩下部分實質上為液體載劑;及任意地5)鹼;6)表面活性劑;7)安定劑;8)腐蝕抑制劑;及9)緩衝劑;其中該多官能基胺係一分子中具有多於一胺基的胺或聚胺;該多官能基酸係一分子中具有多於一羧酸根的酸或多元酸;至少一多官能基酸中的至少一個不具有芳香族部份;該多官能基酸及該多官能基胺中的一個係非聚合性;及該液體載劑係選自由有機溶劑、水及其組合所組成的群組。
- 如申請專利範圍第1項之金屬腐蝕抑制的清潔組合物,其中該多官能基胺係選自由聚乙烯亞胺、三胺、五胺、六胺及其組合所組成的群組。
- 如申請專利範圍第1項之金屬腐蝕抑制的清潔組合物,其中該多官能基酸係選自由以下所組成的群組:(i)不具有芳香族部份的二羧酸、具有芳香族部分的二羧酸及其組合;(ii)不具有芳香族部份的三羧酸、具有芳香族部分的三羧酸及其組合;及(iii)不具有芳香族部份的四羧酸、具有芳香族部分的四羧酸及其組合。
- 如申請專利範圍第3項之金屬腐蝕抑制的清潔組合物,其中該不具有芳香族部份的二羧酸係選自由丙二酸、蘋果酸及其組合所組成的群組;該具有芳香族部分的二羧酸係苯二甲酸;該不具有芳香族部份的三羧酸係檸檬酸;該具有芳香族部分的三羧酸係偏苯三甲酸;該不具有芳香族部份的四羧酸係乙二胺四醋酸(EDTA);而且該具有芳香族部分的四羧酸係苯均四酸。
- 如申請專利範圍第1項之金屬腐蝕抑制的清潔組合物,其中該有機溶劑係選自由丙二醇(PG)、二醇醚類、N-甲基吡咯烷酮(NMP)、二甲基亞碸(DMSO)、二甲基乙醯胺(DMAC)、環丁碸、二甲基甲醯胺(DMF)及其組合所組成的群組;而且該有機溶劑佔至高70重量%,以組合物的總重量為基準。
- 如申請專利範圍第1項之金屬腐蝕抑制的清潔組合物,其中該氟化物來源係選自由氫氟酸(HF)、氟化銨(NH4F)、二氟化銨(NH4HF2)、氟化四甲基銨(TMAF)及其組合所組成的群組;而且該氟化物來源佔0.01重量%至1.0重量%,以組合物的總重量為基準;該鹼係選自由三乙醇胺(TEA)及經取代的衍生物、二乙醇胺及經取代的衍生物、單乙醇胺及經取代的衍生物及其組合所組成的群組;而且該鹼佔至高50重量%,以組合物的總重量為基準。
- 如申請專利範圍第1項之金屬腐蝕抑制的清潔組合物,其中該金屬腐蝕抑制清潔組合物的pH介於5至10。
- 一種清潔半導體晶圓之方法,其包含:a)提供至少一表面含有至少一金屬和殘餘物的半導體晶圓;b)提供金屬腐蝕抑制的清潔組合物,其由下列組成:1)0.1重量%至5重量%的至少一多官能基酸,以組合物的總重量為基準;2)0.1至25重量%的至少一多官能基胺,以組合物的總重量為基準;3)0.01重量%至5.7重量%的氟化物來源;4)剩下部分實質上為液體載劑;及任意地5)鹼;6)表面活性劑;7)安定劑;8)腐蝕抑制劑;及9)緩衝劑;其中該多官能基胺係一分子中具有多於一胺基的胺或聚胺;該多官能基酸係一分子中具有多於一羧酸根的酸或多元酸;至少一多官能基酸中的至少一個不具有芳香族部份;該多官能基酸及該多官能基胺中的一個係非聚合性;及該液體載劑係選自由有機溶劑、水及其組合所組成的群組;c)使該半導體晶圓與該金屬腐蝕抑制的清潔組合物接觸;及d)清潔該等殘餘物;其中使具有殘餘物的至少一部分表面與該金屬腐蝕抑制的組合物接觸。
- 如申請專利範圍第8項之清潔半導體晶圓之方法,其中該金屬係選自由銅(Cu)、鎢(W)、鈦(Ti)、鉭(Ta)、鈷(Co)及鋁(Al)及其組合所組成的群組;該等殘餘物係在高密度電漿蝕刻之後繼而以含氧電漿灰化而衍生;而且衍生自化學機械拋光(CMP)。
- 如申請專利範圍第8項之清潔半導體晶圓之方法,其中該金屬係銅(Cu)。
- 如申請專利範圍第8項之清潔半導體晶圓之方法,其中該多官能基胺係選自由聚乙烯亞胺、三胺、五胺、六胺及其組合所組成的群組;該多官能基酸係選自由以下所組成的群組:(i)不具有芳香族部份的二羧酸、具有芳香族部分的二羧酸及其組合;(ii)不具有芳香族部份的三羧酸、具有芳香族部分的三羧酸及其組合;及(iii)不具有芳香族部份的四羧酸、具有芳香族部分的四羧酸及其組合;及該有機溶劑係選自由丙二醇(PG)、二醇醚類、N-甲基吡咯烷酮(NMP)、二甲基亞碸(DMSO)、二甲基乙醯胺(DMAC)、環丁碸、二甲基甲醯胺(DMF)及其組合所組成的群組;而且該有機溶劑佔至高70重量%,以組合物的總重量為基準。
- 如申請專利範圍第11項之清潔半導體晶圓之方法,其中該不具有芳香族部份的二羧酸係選自由丙二酸、蘋果酸及其組合所組成的群組;該具有芳香族部分的二羧酸係苯二甲酸;該不具有芳香族部份的三羧酸係檸檬酸;該具有芳香族部分的三羧酸係偏苯三甲酸;該不具有芳香族部份的四羧酸係乙二胺四醋酸(EDTA);而且該具有芳香族部分的四羧酸係苯均四酸。
- 如申請專利範圍第8項之清潔半導體晶圓之方法,其中該金屬腐蝕抑制的清潔組合物的pH介於5至10。
- 如申請專利範圍第8項之清潔半導體晶圓之方法,其中該氟化物來源係選自由氫氟酸(HF)、氟化銨(NH4F)、二氟化銨(NH4HF2)、氟化四甲基銨(TMAF)及其組合所組成的群組;而且該氟化物來源佔0.01重量%至1.0重量%,以組合物的總重量為基準;該鹼係選自由三乙醇胺(TEA)及經取代的衍生物、二乙醇胺及經取代的衍生物、單乙醇胺及經取代的衍生物及其組合所組成的群組;而且該鹼佔至高50重量%,以組合物的總重量為基準。
- 一種半導體晶圓清潔系統,其包含:一半導體晶圓,其至少一表面含有至少一金屬和殘餘物;一金屬腐蝕抑制的清潔組合物,其由下列組成:1)0.1重量%至5重量%的至少一多官能基酸,以組合物的總重量為基準;2)0.1至25重量%的至少一多官能基胺,以組合物的總重量為基準;3)0.01重量%至5.7重量%的氟化物來源;4)剩下部分實質上為液體載劑;及任意地5)鹼;6)表面活性劑;7)安定劑;8)腐蝕抑制劑;及9)緩衝劑;其中該多官能基胺係一分子中具有多於一胺基的胺或聚胺;該多官能基酸係一分子中具有多於一羧酸根的酸或多元酸;至少一多官能基酸中的至少一個不具有芳香族部份;該多官能基酸及該多官能基胺中的一個係非聚合性;及該液體載劑係選自由有機溶劑水及其組合所組成的群組;其中使具有殘餘物的至少一部分表面與該清潔組合物接觸。
- 如申請專利範圍第15項之半導體晶圓清潔系統,其中該金屬係選自由銅(Cu)、鎢(W)、鈦(Ti)、鉭(Ta)、鈷(Co)及鋁(Al)及其組合所組成的群組;該等殘餘物係在高密度電漿蝕刻之後繼而以含氧電漿灰化而衍生;而且衍生自化學機械拋光(CMP)。
- 如申請專利範圍第15項之半導體晶圓清潔系統,其中該金屬係銅(Cu)。
- 如申請專利範圍第15項之半導體晶圓清潔系統,其中該多官能基胺係選自由聚乙烯亞胺、三胺、五胺、六胺及其組合所組成的群組;該多官能基酸係選自由以下所組成的群組:(i)不具有芳香族部份的二羧酸、具有芳香族部分的二羧酸及其組合;(ii)不具有芳香族部份的三羧酸、具有芳香族部分的三羧酸及其組合;及(iii)不具有芳香族部份的四羧酸、具有芳香族部分的四羧酸及其組合;及該有機溶劑係選自由丙二醇(PG)、二醇醚類、N-甲基吡咯烷酮(NMP)、二甲基亞碸(DMSO)、二甲基乙醯胺(DMAC)、環丁碸、二甲基甲醯胺(DMF)及其組合所組成的群組;而且該有機溶劑佔至高70重量%,以組合物的總重量為基準。
- 如申請專利範圍第18項之半導體晶圓清潔系統,其中該不具有芳香族部份的二羧酸係選自由丙二酸、蘋果酸及其組合所組成的群組;該具有芳香族部分的二羧酸係苯二甲酸;該不具有芳香族部份的三羧酸係檸檬酸;該具有芳香族部分的三羧酸係偏苯三甲酸;該不具有芳香族部份的四羧酸係乙二胺四醋酸(EDTA);而且該具有芳香族部分的四羧酸係苯均四酸。
- 如申請專利範圍第15項之半導體晶圓清潔系統,其中該金屬腐蝕抑制的清潔組合物的pH介於5至10。
- 如申請專利範圍第1項之金屬腐蝕抑制的清潔組合物,其中該氟化物來源不包括氟化銨。
- 如申請專利範圍第8項之清潔半導體晶圓之方法,其中該金屬腐蝕抑制的清潔組合物中的氟化物來源不包括氟化銨。
- 如申請專利範圍第15項之半導體晶圓清潔系統,其中該金屬腐蝕抑制的清潔組合物中的氟化物來源不包括氟化銨。
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JP2016021573A (ja) | 2016-02-04 |
IL239853B (en) | 2022-01-01 |
US20160010035A1 (en) | 2016-01-14 |
EP2975108B1 (en) | 2018-04-18 |
SG10201505491UA (en) | 2016-02-26 |
KR20160008478A (ko) | 2016-01-22 |
KR101874556B1 (ko) | 2018-07-05 |
CN105261554A (zh) | 2016-01-20 |
TW201602413A (zh) | 2016-01-16 |
CN105261554B (zh) | 2018-08-21 |
US9957469B2 (en) | 2018-05-01 |
EP2975108A1 (en) | 2016-01-20 |
JP6117866B2 (ja) | 2017-04-19 |
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