WO1998030667A1 - Semiconductor wafer cleaning composition and method with aqueous ammonium fluoride and amine - Google Patents
Semiconductor wafer cleaning composition and method with aqueous ammonium fluoride and amine Download PDFInfo
- Publication number
- WO1998030667A1 WO1998030667A1 PCT/US1998/000392 US9800392W WO9830667A1 WO 1998030667 A1 WO1998030667 A1 WO 1998030667A1 US 9800392 W US9800392 W US 9800392W WO 9830667 A1 WO9830667 A1 WO 9830667A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- fluoride
- group
- ammonium
- chosen
- cleaning formulation
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 68
- 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 title claims abstract description 44
- 150000001412 amines Chemical class 0.000 title claims abstract description 35
- 238000004140 cleaning Methods 0.000 title claims abstract description 29
- 239000004065 semiconductor Substances 0.000 title claims abstract description 11
- 238000000034 method Methods 0.000 title claims description 18
- 238000009472 formulation Methods 0.000 claims abstract description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000002738 chelating agent Substances 0.000 claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 claims abstract description 28
- 239000002184 metal Substances 0.000 claims abstract description 28
- 238000004380 ashing Methods 0.000 claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 40
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 40
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 37
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 claims description 34
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 30
- GIAFURWZWWWBQT-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanol Chemical compound NCCOCCO GIAFURWZWWWBQT-UHFFFAOYSA-N 0.000 claims description 22
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 19
- VSWDORGPIHIGNW-UHFFFAOYSA-N Pyrrolidine dithiocarbamic acid Chemical compound SC(=S)N1CCCC1 VSWDORGPIHIGNW-UHFFFAOYSA-N 0.000 claims description 16
- 125000001931 aliphatic group Chemical group 0.000 claims description 15
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 15
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 14
- IKGLACJFEHSFNN-UHFFFAOYSA-N hydron;triethylazanium;trifluoride Chemical compound F.F.F.CCN(CC)CC IKGLACJFEHSFNN-UHFFFAOYSA-N 0.000 claims description 14
- MOVBJUGHBJJKOW-UHFFFAOYSA-N methyl 2-amino-5-methoxybenzoate Chemical compound COC(=O)C1=CC(OC)=CC=C1N MOVBJUGHBJJKOW-UHFFFAOYSA-N 0.000 claims description 14
- GSEJCLTVZPLZKY-UHFFFAOYSA-O triethanolammonium Chemical compound OCC[NH+](CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-O 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 9
- WRQNANDWMGAFTP-UHFFFAOYSA-N Methylacetoacetic acid Chemical compound COC(=O)CC(C)=O WRQNANDWMGAFTP-UHFFFAOYSA-N 0.000 claims description 8
- GCPWJFKTWGFEHH-UHFFFAOYSA-N acetoacetamide Chemical compound CC(=O)CC(N)=O GCPWJFKTWGFEHH-UHFFFAOYSA-N 0.000 claims description 8
- BVCZEBOGSOYJJT-UHFFFAOYSA-N ammonium carbamate Chemical compound [NH4+].NC([O-])=O BVCZEBOGSOYJJT-UHFFFAOYSA-N 0.000 claims description 8
- KXDHJXZQYSOELW-UHFFFAOYSA-N carbonic acid monoamide Natural products NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 8
- BEPAFCGSDWSTEL-UHFFFAOYSA-N dimethyl malonate Chemical compound COC(=O)CC(=O)OC BEPAFCGSDWSTEL-UHFFFAOYSA-N 0.000 claims description 8
- LROATHSBUUYETB-UHFFFAOYSA-M tetramethylazanium;2,2,2-trifluoroacetate Chemical compound C[N+](C)(C)C.[O-]C(=O)C(F)(F)F LROATHSBUUYETB-UHFFFAOYSA-M 0.000 claims description 8
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 7
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000004429 atom Chemical group 0.000 claims description 4
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims description 4
- 238000001020 plasma etching Methods 0.000 claims description 4
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 claims 13
- 229960002447 thiram Drugs 0.000 claims 13
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims 6
- ATWLCPHWYPSRBQ-UHFFFAOYSA-N N-Methylacetoacetamide Chemical compound CNC(=O)CC(C)=O ATWLCPHWYPSRBQ-UHFFFAOYSA-N 0.000 claims 6
- ZUHZZVMEUAUWHY-UHFFFAOYSA-N n,n-dimethylpropan-1-amine Chemical compound CCCN(C)C ZUHZZVMEUAUWHY-UHFFFAOYSA-N 0.000 claims 6
- LTSORXKZGSXNHL-UHFFFAOYSA-M tetramethylazanium;thiobenzate Chemical compound C[N+](C)(C)C.[O-]C(=S)C1=CC=CC=C1 LTSORXKZGSXNHL-UHFFFAOYSA-M 0.000 claims 6
- 238000005530 etching Methods 0.000 claims 2
- 235000012431 wafers Nutrition 0.000 description 11
- 210000002381 plasma Anatomy 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 229910052814 silicon oxide Inorganic materials 0.000 description 6
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- -1 Dimethyl malonate Methyl acetoacetate N-Methyl acetoacetamide 2,4-Pentanedione Chemical compound 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- MUMGGOZAMZWBJJ-DYKIIFRCSA-N Testostosterone Chemical compound O=C1CC[C@]2(C)[C@H]3CC[C@](C)([C@H](CC4)O)[C@@H]4[C@@H]3CCC2=C1 MUMGGOZAMZWBJJ-DYKIIFRCSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical class [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 150000004706 metal oxides Chemical group 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- GTDKXDWWMOMSFL-UHFFFAOYSA-M tetramethylazanium;fluoride Chemical compound [F-].C[N+](C)(C)C GTDKXDWWMOMSFL-UHFFFAOYSA-M 0.000 description 2
- PTMFUWGXPRYYMC-UHFFFAOYSA-N triethylazanium;formate Chemical compound OC=O.CCN(CC)CC PTMFUWGXPRYYMC-UHFFFAOYSA-N 0.000 description 2
- PVXVWWANJIWJOO-UHFFFAOYSA-N 1-(1,3-benzodioxol-5-yl)-N-ethylpropan-2-amine Chemical compound CCNC(C)CC1=CC=C2OCOC2=C1 PVXVWWANJIWJOO-UHFFFAOYSA-N 0.000 description 1
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 1
- QIERHPPHZKFQRT-UHFFFAOYSA-N 2-aminoethanol;n,n-dimethylpropan-1-amine Chemical compound NCCO.CCCN(C)C QIERHPPHZKFQRT-UHFFFAOYSA-N 0.000 description 1
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- QMMZSJPSPRTHGB-UHFFFAOYSA-N MDEA Natural products CC(C)CCCCC=CCC=CC(O)=O QMMZSJPSPRTHGB-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- WPPDFTBPZNZZRP-UHFFFAOYSA-N aluminum copper Chemical compound [Al].[Cu] WPPDFTBPZNZZRP-UHFFFAOYSA-N 0.000 description 1
- SXDNSMYNMVYSKQ-UHFFFAOYSA-N azanium;3-oxobutanamide;carbamate Chemical compound [NH4+].NC([O-])=O.CC(=O)CC(N)=O SXDNSMYNMVYSKQ-UHFFFAOYSA-N 0.000 description 1
- 239000006172 buffering agent Substances 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
- G03F7/422—Stripping or agents therefor using liquids only
- G03F7/425—Stripping or agents therefor using liquids only containing mineral alkaline compounds; containing organic basic compounds, e.g. quaternary ammonium compounds; containing heterocyclic basic 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
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/10—Salts
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/26—Organic compounds containing oxygen
- C11D7/264—Aldehydes; Ketones; Acetals or ketals
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/26—Organic compounds containing oxygen
- C11D7/265—Carboxylic acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/26—Organic compounds containing oxygen
- C11D7/266—Esters or carbonates
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
- C11D7/3209—Amines or imines with one to four nitrogen atoms; Quaternized amines
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
- C11D7/3218—Alkanolamines or alkanolimines
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
- C11D7/3245—Aminoacids
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
- C11D7/3263—Amides or imides
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
- C11D7/3281—Heterocyclic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/34—Organic compounds containing sulfur
-
- 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
- H01L21/02063—Cleaning during device manufacture during, before or after processing of insulating layers the processing being the formation of vias or contact holes
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/14—Hard surfaces
- C11D2111/22—Electronic devices, e.g. PCBs or semiconductors
Definitions
- the present invention relates generally to chemical formulations used in semiconductor wafer fabrication and particularly to chemical formulations that are utilized to remove residue from wafers following a resist plasma ashing step.
- the prior art teaches the utilization of various chemical formulations to remove residue and clean wafers following a resist ashing step.
- Some of these prior art chemical formulations include akaline compositions containing amines and/or tetraalkyl ammonium hydroxides, water and/or other solvents, and chelating agents. Still other formulations are based on acidic to neutral solutions containing ammonium fluoride.
- the various prior art formulations have drawbacks which include unwanted removal of metal or insulator layers and the corrosion of desirable metal layers, particularly aluminum and aluminum-copper alloys and titanium nitride features. There is therefore a need for chemical formulations which effectively remove residue following a resist ashing step which do not attack and potentially degrade delicate structures which are meant to remain on a wafer.
- a semiconductor wafer cleaning formulation for use in post plasma ashing semiconductor fabrication comprising the following components in the percentage by weight ranges shown:
- Ammonium fluoride and/or a derivative thereof 1 -21 % an organic amine or mixture of two amines; 20-55% water; 23-50% a metal chelating agent or mixture of chelating agents. 0-21 %
- the present invention comprises formulations that are suitable for stripping inorganic wafer residues which originate from high density plasma etching followed by ashing with oxygen-containing plasmas.
- the formulations are also suitable for removing slurry particles of aluminum oxides and other oxides remaining after CMP (chemical mechanical polishing).
- the formulations contain ammonium fluoride or a derivative of ammonium fluoride, an amine or mixture of amines, water and, optionally, one or more metal chelating agents.
- the preferred formulations utilize the following components (percentages are by weight):
- Ammonium fluoride and/or a derivative thereof 1-21 %
- the preferred amines are: Diglycolamine (DGA) Methyldiethanolamine (MDEA)
- the preferred fluoride sources are: Ammonium fluoride
- Triethanolammonium fluoride TEAF
- fluoride sources that are effective include: Diglycolammonium fluoride (DGAF) Tetramethylammonium fluoride (TMAF)
- the metal chelating agents that are effective include: Acetoacetamide Ammonium carbamate
- TMTDS Tetramethylammonium thiobenzoate Tetramethylammonium trifluoroacetate Tetramethylthiuram disulfide
- ammonium fluoride or a substituted fluoride source as identified above with an amine provides better stripping performance with less corrosivity than formulations containing ammonium fluoride without amines and formulations containing amines without ammonium fluoride.
- the resulting alkaline solutions were effective at lower processing temperatures (21°-40° C) than conventional amine-containing formulations.
- the use of 1 ,3-dicarbonyl compounds as chelating agents and to prevent metal corrosion also appears to increase effectiveness.
- amines are limited to 1% or less of the formulation and serve only as surfactants, or amines are not utilized as formulation ingredients at all. Also, the prior art formulations are acidic (pH ⁇ 7). In the formulations of the present invention the amines are present as major components and play major roles in stripping, and the formulations are basic
- R 2 R 3 R 4 NF Hydrogen atoms and/or aliphatic groups.
- metal chelating agents including:
- R is either a Hydrogen atom or an aliphatic group
- X and Y are functional groups containing multiply bonded moities known to have electron-withdrawing properties, for example X and Y may be CONH 2, CONHR', CN, NO 2 , SOR', SO 2 Z in which R' represents an alkyl group and Z represents another atom or group. X and Y may be identical or different.
- amine trifluoroacetates are also expected to be suitable as chelating agents. These would have the general formula, R 1 R 2 R 3 R 4 N + O 2 CCF 3 in which the R groups are Hydrogen atoms and/or aliphatic groups. D. It would also be expected that inclusion of optional components such as surfactants, stabilizers, corrosion inhibitors, buffering agents, and cosolvents would constitute obvious additions to those practiced in the art.
- the formulations of the present invention are particularly useful on wafers which have been etched with chlorine- or fluorine-containing plasmas followed by oxygen plasma ashing.
- the residues generated by this type of processing typically contain inorganic materials such as, but not limited to, aluminum oxide, titanium oxide and aluminum fluoride. These residues are often difficult to dissolve completely without causing corrosion of metal and titanium nitride features required for effective device performance. Also, metal oxide and silicon oxide slurry particles remaining after CMP will also be effectively removed by these formulations.
- Three types of commercially generated wafers containing via structures were evaluated using the formulations of the present invention.
- micron diameter, four layer vias comprised of silicon oxide top and second layers, a third layer of titanium nitride, and a bottom layer of aluminum, silicon, copper (AlSiCu) alloy.
- the substrate was silicon oxide.
- One micron diameter, two-layer vias comprised of a top layer of silicon oxide
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Abstract
A semiconductor wafer cleaning formulation for use in post plasma ashing semiconductor fabrication comprising the following components in the percentage by weight ranges shown: ammonium fluoride and/or a derivative thereof 1-21 %; an organic amine or mixture of two amines 20-55 %; water 23-50 %; a metal chelating agent or mixture of chelating agents 0-21 %.
Description
Specification
SEMICONDUCTOR WAFER CLEANING COMPOSITION AND METHOD WITH AQUEOUS AMMONIUM FLUORIDE AND AMINE
BACKGROUND OF THE INVENTION
Field of the Invention
The present invention relates generally to chemical formulations used in semiconductor wafer fabrication and particularly to chemical formulations that are utilized to remove residue from wafers following a resist plasma ashing step.
Description of the Prior Art
The prior art teaches the utilization of various chemical formulations to remove residue and clean wafers following a resist ashing step. Some of these prior art chemical formulations include akaline compositions containing amines and/or tetraalkyl ammonium hydroxides, water and/or other solvents, and chelating agents. Still other formulations are based on acidic to neutral solutions containing ammonium fluoride. The various prior art formulations have drawbacks which include unwanted removal of metal or insulator layers and the corrosion of desirable metal layers, particularly aluminum and aluminum-copper alloys and titanium nitride features. There is therefore a need for chemical formulations which effectively remove residue following a resist ashing step which do not attack and potentially degrade delicate structures which are meant to remain on a wafer.
SUMMARY OF THE INVENTION
A semiconductor wafer cleaning formulation for use in post plasma ashing semiconductor fabrication comprising the following components in the percentage by weight ranges shown:
Ammonium fluoride and/or a derivative thereof; 1 -21 % an organic amine or mixture of two amines; 20-55% water; 23-50% a metal chelating agent or mixture of chelating agents. 0-21 %
It is an advantage of the present invention that it effectively removes inorganic residues following a plasma ashing step.
It is another advantage of the present invention that it effectively removes metal halide and metal oxide residues following plasma ashing.
It is a further advantage of the present invention that it effectively removes slurry particles of aluminum oxides and other oxides remaining after CMP (chemical mechanical polishing).
It is yet another advantage of the present invention that it provides better stripping performance with less corrosivity than formulations containing ammonium fluoride without amines and amines without ammonium fluoride.
It is yet a further advantage of the present invention that it provides better stripping performance at lower processing temperatures than conventional amine-containing formulations.
It is still a further advantage of the present invention that it includes a chelating agent to prevent metal corrosion and increase stripping effectiveness.
These and other features and advantages of the present invention will become understood to those of ordinary skill in the art upon review of the following detailed description of the preferred embodiments.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention comprises formulations that are suitable for stripping inorganic wafer residues which originate from high density plasma etching followed by ashing with oxygen-containing plasmas. The formulations are also suitable for removing slurry particles of aluminum oxides and other oxides remaining after CMP (chemical mechanical polishing). The formulations contain ammonium fluoride or a derivative of ammonium fluoride, an amine or mixture of amines, water and, optionally, one or more metal chelating agents. The preferred formulations utilize the following components (percentages are by weight):
Ammonium fluoride and/or a derivative thereof: 1-21 %
An organic amine or mixture of two amines 20-55%
Water 23-50% A Metal chelating agent or mixture of chelating agents: 0-21 %
The preferred amines are: Diglycolamine (DGA) Methyldiethanolamine (MDEA)
Pentamethyldiethylenetriamine (PMDETA)
Triethanolamine (TEA) Triethylenediamine (TEDA)
Other amines that are effective include: Hexamethylenetetramine
3, 3-lminobis (N,N-dimethylpropylamine) Monoethanolamine
The preferred fluoride sources are: Ammonium fluoride
Triethanolammonium fluoride (TEAF)
Other fluoride sources that are effective include: Diglycolammonium fluoride (DGAF) Tetramethylammonium fluoride (TMAF)
Triethylamine tris (hydrogen fluoride) (TREAT-HF)
The metal chelating agents that are effective include: Acetoacetamide Ammonium carbamate
Ammonium pyrrolidinedithiocarbamate (APDC) Dimethyl malonate Methyl acetoacetate N-Methyl acetoacetamide 2,4-Pentanedione
Tetramethylammonium thiobenzoate Tetramethylammonium trifluoroacetate Tetramethylthiuram disulfide (TMTDS)
The combination of ammonium fluoride or a substituted fluoride source as identified above with an amine (other than as a surfactant in an amount of 1 % or less) provides better stripping performance with less corrosivity than formulations containing ammonium fluoride without amines and formulations containing amines without ammonium fluoride. In addition, the resulting alkaline solutions were effective at lower processing temperatures (21°-40° C) than conventional amine-containing formulations.
The use of 1 ,3-dicarbonyl compounds as chelating agents and to prevent metal corrosion also appears to increase effectiveness.
In the prior art amines are limited to 1% or less of the formulation and serve only as surfactants, or amines are not utilized as formulation ingredients at all. Also, the prior art formulations are acidic (pH < 7). In the formulations of the present invention the amines are present as major components and play major roles in stripping, and the formulations are basic
(pH > 7).
Several representative examples of preferred formulations are:
Triethanolamine 45% Ammonium fluoride 5%
Water 50%
Diglycolamine 55%
Ammonium fluoride 5% 2,4-Pentanedione 10%
Water 30%
Triethanolamine 27.1%
TEAF 20.3% 2,4-Pentanedione 10%
Water 42.6%
PMDETA 45%
Ammonium fluoride 5% Methyl acetoacetate 6%
Water 44%
PMDETA 45%
Ammonium fluoride 1% 2,4-Pentanedione 8%
APDC 15%
Water 31 %
PMDETA 55% Ammonium fluoride 1%
Dimethyl malonate 13.2%
TMTDS 6% Water 24.8%
TEA 36%
PMDETA 16%
Ammonium fluoride 12%
Acetoacetamide 10%
Water 28%
TEA 45%
Ammonium fluoride 11.4%
Tetramethylammonium-trifluoroacetate 17%
Water 27%
Triethanolamine 45-52% Ammonium fluoride 3-10% 2,4-Pentanedione 5-10% Water 35-44%
PMDETA 38-45%
Ammonium fluoride 5% 2,4-Pentanedione 10% Water 40-47%
PMDETA 38% TMAF 5%
Ammonium fluoride 2% 2,4-Pentanedione 10% Water 45%
PMDETA 38%
Ammonium fluoride 1 % 2,4-Pentanedione 10.7% Ammonium carbamate 10% Water 38.3%
The inventors expect that closely related ingredients would be expected to show comparable performance to those utilized in our formulations.
These include:
A. Other organic amines are expected to be suitable. B. Other substituted ammonium fluorides are expected to be suitable. These would have the general formula, R-|R2R3R4NF in which the R groups are Hydrogen atoms and/or aliphatic groups.
C. Other metal chelating agents including:
1. Other 1 ,3-dicarbonyl compounds are expected to display comparable performance. These would have the following general structure:
X-CHR-Y in which
R is either a Hydrogen atom or an aliphatic group and
X and Y are functional groups containing multiply bonded moities known to have electron-withdrawing properties, for example X and Y may be CONH2, CONHR', CN, NO2, SOR', SO2Z in which R' represents an alkyl group and Z represents another atom or group. X and Y may be identical or different.
2. Other amine trifluoroacetates are also expected to be suitable as chelating agents. These would have the general formula, R1R2R3R4N+ O2CCF3 in which the R groups are Hydrogen atoms and/or aliphatic groups. D. It would also be expected that inclusion of optional components such as surfactants, stabilizers, corrosion inhibitors, buffering agents, and cosolvents would constitute obvious additions to those practiced in the art.
The formulations of the present invention are particularly useful on wafers which have been etched with chlorine- or fluorine-containing plasmas followed by oxygen plasma ashing. The residues generated by this type of processing typically contain inorganic materials such as, but not limited to, aluminum oxide, titanium oxide and aluminum fluoride. These residues are often difficult to dissolve completely without causing corrosion of metal and titanium nitride features required for effective device performance. Also, metal oxide and silicon oxide slurry particles remaining after CMP will also be effectively removed by these formulations. Three types of commercially generated wafers containing via structures were evaluated using the formulations of the present invention. In each case, following plasma etching and ashing, immersion of wafers in the formulation of the present invention was performed in baths at 21-60°C for 10-30 minutes (preferred: 21-35°C for 20-30 minutes) followed by washing with deionized water and drying with a stream of nitrogen gas. It is expected that the formulations can also be applied by spraying onto the wafers in an automated spray tool followed by a water rinse.
The three via structures were:
1. 0.8 micron diameter, four layer vias comprised of silicon oxide top and second layers, a third layer of titanium nitride, and a bottom layer of aluminum, silicon, copper (AlSiCu) alloy. The substrate was silicon oxide. 2. One micron diameter, two-layer vias comprised of a top layer of silicon oxide
(7000 Angs. thick) and a bottom layer of titanium nitride (1200 Angs. thick) on top of a silicon substrate.
3. 1.6 micron wide, 4-layer vias with a top layer of titanium nitride (40 Nm. thick), a second layer of silicon oxide (1.3 microns thick), and a bottom layer of aluminum/copper on a silicon oxide substrate.
The present formulations were rated according to relative stripping effectiveness and corrosivity of the formulations. The preferred formulations scored best and, in overall performance based on both stripping effectiveness and low corrosivity, are approximately equal. While the present invention has been described with reference to certain preferred embodiments, it will be understood by those skilled in the art that various alterations and modifications may be made therein without departing from the true spirit and scope of the invention. It is therefore intended that the following claims cover all such alterations and modifications which nevertheless include the true spirit and scope of the invention. What I claim is:
Claims
1. A semiconductor wafer cleaning formulation for use in post plasma ashing semiconductor fabrication comprising the following components in the percentage by weight ranges shown: a fluoride source; 1-21 % at least one organic amine; 20-55% water; 23-50% at least one metal chelating agent. 0-21%.
2. A cleaning formulation as described in claim 1 wherein said fluoride source is chosen from the group consisting of:
Ammonium fluoride; and Triethanolammonium fluoride (TEAF).
3. A cleaning formulation as described in claim 1 wherein said organic amine is chose from the group consisting of:
Diglycolamine (DGA), Methyldiethanolamine (MDEA), Pentamethyldiethylenetriamine (PMDETA),
Triethanolamine (TEA), and Triethylenediamine (TEDA).
4. A cleaning formulation as described in claim 1 wherein said metal chelating agent is chosen from the group consisting of:
Acetoacetamide, Ammonium carbamate, Ammonium pyrrolidinedithiocarbamate (APDC),
Dimethyl malonate, Methyl acetoacetate, N-Methyl acetoacetamide, 2,4-Pentanedione, Tetramethylammonium thiobenzoate,
Tetramethylammonium trifluoroacetate, and Tetramethylthiuram disulfide (TMTDS).
5. A cleaning formulation as described in claim 1 wherein said fluoride source is chosen from the group consisting of:
Ammonium fluoride, Triethanolammonium fluoride (TEAF), Diglycolammonium fluoride (DGAF),
Tetramethylammonium fluoride (TMAF), and Triethylamine tris (hydrogen fluoride) (TREAT-HF).
6. A cleaning formulation as described in claim 1 wherein said organic amine is chosen from the group consisting of:
Diglycolamine (DGA), Methyldiethanolamine (MDEA), Pentamethyldiethylenetriamine (PMDETA),
Triethanolamine (TEA), Triethylenediamine (TEDA), Hexamethylenetetramine, 3, 3-lminobis (N,N-dimethylpropylamine), and Monoethanolamine.
7. A cleaning formulation as described in claim 1 wherein said fluoride source is chosen from the group consisting of:
Ammonium fluoride,
Triethanolammonium fluoride (TEAF), Diglycolammonium fluoride (DGAF),
Tetramethylammonium fluoride (TMAF), and
Triethylamine tris (hydrogen fluoride) (TREAT-HF); said organic amine is chosen from the group consisting of:
Diglycolamine (DGA), Methyldiethanolamine (MDEA),
Pentamethyldiethylenetriamine (PMDETA),
Triethanolamine (TEA),
Triethylenediamine (TEDA),
Hexamethylenetetramine, 3, 3-lminobis (N,N-dimethylpropylamine), and
Monoethanolamine; and said metal chelating agent is chosen from the group consisting of: Acetoacetamide, Ammonium carbamate,
Ammonium pyrrolidinedithiocarbamate (APDC), Dimethyl malonate, Methyl acetoacetate,
N-Methyl acetoacetamide, 2,4-Pentanedione,
Tetramethylammonium thiobenzoate, Tetramethylammonium trifluoroacetate, and Tetramethylthiuram disulfide (TMTDS).
8. A cleaning formulation as described in claim 1 wherein said fluoride source has the general formula R1R2R3R4NF in which the R groups are hydrogen atoms and/or aliphatic groups, and wherein said metal chelating agent would have the following general structure:
X-CHR-Y in which R is either a hydrogen atom or an aliphatic group and
X and Y are functional groups containing multiply bonded moities known to have electron-withdrawing properties, wherein X and Y may be CONH2, CONHR', CN, NO2, SOR', SO2Z in which R' represents an alkyl group and Z represents another atom or group, and wherein X and Y may be identical or different.
9. A cleaning formulation as described in claim 1 wherein said fluoride source4 has the general formula R1R2R3R4NF in which the R groups are hydrogen atoms and/or aliphatic groups, and wherein said metal chelating agent would have the general formula, R-|R2R3R4N+ " O2CCF3 in which the R groups are hydrogen atoms and/or aliphatic groups.
10. A cleaning formulation as described in claim 1 being comprised of: Triethanolamine 45% Ammonium fluoride 5% Water 50%.
11. A cleaning formulation as described in claim 1 being comprised of: Diglycolamine 55% Ammonium fluoride 5% 2,4-Pentanedione 10% Water 30%.
12. A cleaning formulation as described in claim 1 being comprised of: Triethanolamine 27.1% TEAF 20.3% 2,4-Pentanedione 10% Water 42.6%.
13. A cleaning formulation as described in claim 1 being comprised of: PMDETA 45% Ammonium fluoride 5% Methyl acetoacetate 6% Water 44%.
14. A cleaning formulation as described in claim 1 being comprised of: PMDETA 45% Ammonium fluoride 1% 2,4-Pentanedione 8% APDC 15% Water 31 %.
15. A cleaning formulation as described in claim 1 being comprised of: PMDETA 55% Ammonium fluoride 1% Dimethyl malonate 13.2% TMTDS 6% Water 24.8%.
16. A cleaning formulation as described in claim 1 being comprised of: TEA 36% PMDETA 16% Ammonium fluoride 12% Acetoacetamide 10% Water 28%.
17. A cleaning formulation as described in claim 1 being comprised of: TEA 45% Ammonium fluoride 11.4% Tetramethylammonium-trifluoroacetate 17%
Water 27%.
18. A cleaning formulation as described in claim 1 being comprised of: Triethanolamine 45-52% Ammonium fluoride 3-10% 2,4-Pentanedione 5-10% Water 35-44%.
19. A cleaning formulation as described in claim 1 being comprised of: PMDETA 38-45% Ammonium fluoride 5% 2,4-Pentanedione 10% Water 40-47%.
20. A cleaning formulation as described in claim 1 being comprised of: PMDETA 38% TMAF 5% Ammonium fluoride 2% 2,4-Pentanedione 10%
Water 45%.
21. A cleaning formulation as described in claim 1 being comprised of: PMDETA 38% Ammonium fluoride 1 % 2,4-Pentanedione 10.7% Ammonium carbamate 10%
Water 38.3%.
22. A method for fabricating a semiconductor wafer including the steps comprising: plasma etching a metalized layer from a surface of the wafer; plasma ashing a resist from the surface of the wafer following the metal etching step; cleaning the wafer in a following step using a chemical formulation including the following components in the percentage by weight ranges shown: a fluoride source; 1-21% at least one organic amine; 20-55% water; 23-50% at least one metal chelating agent. 0-21 %.
23. A cleaning formulation as described in claim 22 wherein said fluoride source is chosen from the group consisting of:
Ammonium fluoride; and Triethanolammonium fluoride (TEAF).
24. A method as described in claim 22 wherein said organic amine is chose from the group consisting of:
Diglycolamine (DGA), Methyldiethanolamine (MDEA), Pentamethyldiethylenetriamine (PMDETA),
Triethanolamine (TEA), and Triethylenediamine (TEDA).
25. A method as described in claim 22 wherein said metal chelating agent is chosen from the group consisting of:
Acetoacetamide, Ammonium carbamate, Ammonium pyrrolidinedithiocarbamate (APDC),
Dimethyl malonate, Methyl acetoacetate, N-Methyl acetoacetamide, 2,4-Pentanedione, Tetramethylammonium thiobenzoate,
Tetramethylammonium trifluoroacetate, and Tetramethylthiuram disulfide (TMTDS).
26. A method as described in claim 22 wherein said fluoride source is chosen from the group consisting of:
Ammonium fluoride, Triethanolammonium fluoride (TEAF), Diglycolammonium fluoride (DGAF),
Tetramethylammonium fluoride (TMAF), and Triethylamine tris (hydrogen fluoride) (TREAT-HF).
27. A method as described in claim 22 wherein said organic amine is chosen from the group consisting of:
Diglycolamine (DGA), Methyldiethanolamine (MDEA), Pentamethyldiethylenetriamine (PMDETA),
Triethanolamine (TEA), Triethylenediamine (TEDA), Hexamethylenetetramine, 3, 3-lminobis (N,N-dimethylpropylamine), and Monoethanolamine.
28. A method as described in claim 22 wherein said fluoride source is chosen from the group consisting of:
Ammonium fluoride,
Triethanolammonium fluoride (TEAF), Diglycolammonium fluoride (DGAF),
Tetramethylammonium fluoride (TMAF), and
Triethylamine tris (hydrogen fluoride) (TREAT-HF); said organic amine is chosen from the group consisting of:
Diglycolamine (DGA), Methyldiethanolamine (MDEA),
Pentamethyldiethylenetriamine (PMDETA),
Triethanolamine (TEA),
Triethylenediamine (TEDA),
Hexamethylenetetramine, 3, 3-lminobis (N,N-dimethylpropylamine), and
Monoethanolamine; and said metal chelating agent is chosen from the group consisting of:
Acetoacetamide,
Ammonium carbamate, Ammonium pyrrolidinedithiocarbamate (APDC),
Dimethyl malonate,
Methyl acetoacetate,
N-Methyl acetoacetamide,
2,4-Pentanedione, Tetramethylammonium thiobenzoate, Tetramethylammonium trifluoroacetate, and Tetramethylthiuram disulfide (TMTDS).
29. A method as described in claim 22 wherein said fluoride source has the general formula R-╬╣R2R3R4NF in which the R groups are hydrogen atoms and/or aliphatic groups, and wherein said metal chelating agent would have the following general structure:
X-CHR-Y in which R is either a hydrogen atom or an aliphatic group and
X and Y are functional groups containing multiply bonded moities known to have electron-withdrawing properties, wherein X and Y may be CONH2, CONHR', CN, NO2, SOR', SO2Z in which R' represents an alkyl group and Z represents another atom or group, and wherein X and Y may be identical or different.
30. A method as described in claim 22 wherein said fluoride source has the general formula R1R2R3R4NF in which the R groups are hydrogen atoms and/or aliphatic groups, and wherein said metal chelating agent would have the general formula, R1R2R3R4N+ O2CCF3 in which the R groups are hydrogen atoms and/or aliphatic groups.
31. A method for fabricating a semiconductor wafer including the steps comprising: plasma etching a metalized layer from a surface of the wafer; plasma ashing a resist from the surface of the wafer following the metal etching step; cleaning the wafer in a following step using a chemical formulation including the following components in the percentage by weight ranges shown: a fluoride source; 1-21% at least one organic amine; 20-55% water; 23-50% at least one metal chelating agent. 0-21 %.
32. A cleaning formulation as described in claim 31 wherein said fluoride source is chosen from the group consisting of:
Ammonium fluoride; and Triethanolammonium fluoride (TEAF).
33. A method as described in claim 31 wherein said organic amine is chose from the group consisting of:
Diglycolamine (DGA), Methyldiethanolamine (MDEA), Pentamethyldiethylenetriamine (PMDETA),
Triethanolamine (TEA), and Triethylenediamine (TEDA).
34. A method as described in claim 31 wherein said metal chelating agent is chosen from the group consisting of:
Acetoacetamide, Ammonium carbamate, Ammonium pyrrolidinedithiocarbamate (APDC),
Dimethyl malonate, Methyl acetoacetate, N-Methyl acetoacetamide, 2,4-Pentanedione, Tetramethylammonium thiobenzoate,
Tetramethylammonium trifluoroacetate, and Tetramethylthiuram disulfide (TMTDS).
35. A method as described in claim 31 wherein said fluoride source is chosen from the group consisting of:
Ammonium fluoride, Triethanolammonium fluoride (TEAF), Diglycolammonium fluoride (DGAF),
Tetramethylammonium fluoride (TMAF), and Triethylamine tris (hydrogen fluoride) (TREAT-HF).
36. A method as described in claim 31 wherein said organic amine is chosen from the group consisting of:
Diglycolamine (DGA), Methyldiethanolamine (MDEA), Pentamethyldiethylenetriamine (PMDETA),
Triethanolamine (TEA), Triethylenediamine (TEDA), Hexamethylenetetramine, 3, 3-lminobis (N,N-dimethylpropylamine), and Monoethanolamine.
37. A method as described in claim 31 wherein said fluoride source is chosen from the group consisting of:
Ammonium fluoride,
Triethanolammonium fluoride (TEAF), Diglycolammonium fluoride (DGAF),
Tetramethylammonium fluoride (TMAF), and
Triethylamine tris (hydrogen fluoride) (TREAT-HF); said organic amine is chosen from the group consisting of:
Diglycolamine (DGA), Methyldiethanolamine (MDEA),
Pentamethyldiethylenetriamine (PMDETA),
Triethanolamine (TEA),
Triethylenediamine (TEDA),
Hexamethylenetetramine, 3, 3-lminobis (N,N-dimethylpropylamine), and
Monoethanolamine; and said metal chelating agent is chosen from the group consisting of:
Acetoacetamide,
Ammonium carbamate, Ammonium pyrrolidinedithiocarbamate (APDC),
Dimethyl malonate,
Methyl acetoacetate,
N-Methyl acetoacetamide,
2,4-Pentanedione, Tetramethylammonium thiobenzoate,
Tetramethylammonium trifluoroacetate, and
Tetramethylthiuram disulfide (TMTDS).
38. A method as described in claim 31 wherein said fluoride source has the general formula R-╬╣R2R3R4NF in which the R groups are hydrogen atoms and/or aliphatic groups, and wherein said metal chelating agent would have the following general structure:
X-CHR-Y in which R is either a hydrogen atom or an aliphatic group and
X and Y are functional groups containing multiply bonded moities known to have electron-withdrawing properties, wherein X and Y may be CONH2, CONHR', CN, NO2, SOR', SO2Z in which R' represents an alkyl group and Z represents another atom or group, and wherein X and Y may be identical or different.
39. A method as described in claim 31 wherein said fluoride source has the general formula R1R2R3R4NF in which the R groups are hydrogen atoms and/or aliphatic groups, and wherein said metal chelating agent would have the general formula, R1R2R3R4N+ O2CCF3 in which the R groups are hydrogen atoms and/or aliphatic groups.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP53111898A JP2001508239A (en) | 1997-01-09 | 1998-01-08 | Semiconductor wafer cleaning composition and method using aqueous ammonium fluoride and amine |
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US3419497P | 1997-01-09 | 1997-01-09 | |
| US60/034,194 | 1997-01-09 | ||
| US4482497P | 1997-04-25 | 1997-04-25 | |
| US60/044,824 | 1997-04-25 | ||
| US08/924,021 US6224785B1 (en) | 1997-08-29 | 1997-08-29 | Aqueous ammonium fluoride and amine containing compositions for cleaning inorganic residues on semiconductor substrates |
| US08/924,021 | 1997-08-29 |
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| Publication Number | Publication Date |
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| WO1998030667A1 true WO1998030667A1 (en) | 1998-07-16 |
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| PCT/US1998/000392 WO1998030667A1 (en) | 1997-01-09 | 1998-01-08 | Semiconductor wafer cleaning composition and method with aqueous ammonium fluoride and amine |
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| EP1066365A1 (en) * | 1999-01-27 | 2001-01-10 | Ashland Inc. | Acidic composition containing fluoride for removal of photoresists and etch residues |
| WO2002086045A1 (en) * | 2001-04-19 | 2002-10-31 | Esc, Inc. | Cleaning compositions |
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| US5698503A (en) * | 1996-11-08 | 1997-12-16 | Ashland Inc. | Stripping and cleaning composition |
| US5709756A (en) * | 1996-11-05 | 1998-01-20 | Ashland Inc. | Basic stripping and cleaning composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5466389A (en) * | 1994-04-20 | 1995-11-14 | J. T. Baker Inc. | PH adjusted nonionic surfactant-containing alkaline cleaner composition for cleaning microelectronics substrates |
| JPH08306651A (en) * | 1995-05-09 | 1996-11-22 | Mitsubishi Chem Corp | Alkaline cleaning composition and cleaning method using the composition |
-
1998
- 1998-01-08 WO PCT/US1998/000392 patent/WO1998030667A1/en active Application Filing
- 1998-01-08 JP JP53111898A patent/JP2001508239A/en not_active Withdrawn
-
2007
- 2007-11-08 JP JP2007291278A patent/JP2008066747A/en not_active Ceased
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1066365A1 (en) * | 1999-01-27 | 2001-01-10 | Ashland Inc. | Acidic composition containing fluoride for removal of photoresists and etch residues |
| EP1066365A4 (en) * | 1999-01-27 | 2002-10-09 | Ashland Inc | Acidic composition containing fluoride for removal of photoresists and etch residues |
| US7361631B2 (en) | 1999-01-27 | 2008-04-22 | Air Products And Chemicals, Inc. | Compositions for the removal of organic and inorganic residues |
| WO2000066697A1 (en) * | 1999-05-03 | 2000-11-09 | Ekc Technology, Inc. | Compositions for cleaning organic and plasma etched residues for semiconductor devices |
| JP4498424B2 (en) * | 2001-03-27 | 2010-07-07 | アドバンスド テクノロジー マテリアルズ，インコーポレイテッド | Aqueous cleaning composition containing copper-specific corrosion inhibitor for cleaning inorganic residues on semiconductor substrates |
| EP1381656A1 (en) * | 2001-03-27 | 2004-01-21 | Advanced Technology Materials, Inc. | Aqueous cleaning composition containing copper-specific corrosion inhibitor for cleaning inorganic residues on semiconductor substrate |
| EP1381656A4 (en) * | 2001-03-27 | 2007-06-13 | Advanced Tech Materials | Aqueous cleaning composition containing copper-specific corrosion inhibitor for cleaning inorganic residues on semiconductor substrate |
| CN100343361C (en) * | 2001-03-27 | 2007-10-17 | 高级技术材料公司 | Aqueous cleaning compsn. contg. copper-specific corrosion inhibitor for cleaning inorganic residues on semiconductor substrate |
| JP2008219009A (en) * | 2001-03-27 | 2008-09-18 | Advanced Technology Materials Inc | Aqueous cleaning composition containing copper-specific corrosion inhibitor for cleaning inorganic residues on semiconductor substrate |
| WO2002086045A1 (en) * | 2001-04-19 | 2002-10-31 | Esc, Inc. | Cleaning compositions |
| US6627587B2 (en) | 2001-04-19 | 2003-09-30 | Esc Inc. | Cleaning compositions |
| US6851432B2 (en) | 2001-04-19 | 2005-02-08 | Advanced Technology Materials, Inc. | Cleaning compositions |
| WO2003006598A1 (en) * | 2001-07-09 | 2003-01-23 | Mallinckrodt Baker Inc. | Ammonia-free alkaline microelectronic cleaning compositions with improved substrate compatibility |
| US7682458B2 (en) | 2005-02-03 | 2010-03-23 | Air Products And Chemicals, Inc. | Aqueous based residue removers comprising fluoride |
| US7888302B2 (en) | 2005-02-03 | 2011-02-15 | Air Products And Chemicals, Inc. | Aqueous based residue removers comprising fluoride |
| US7928446B2 (en) | 2007-07-19 | 2011-04-19 | Mitsubishi Chemical Corporation | Group III nitride semiconductor substrate and method for cleaning the same |
| US8022413B2 (en) | 2007-07-19 | 2011-09-20 | Misubishi Chemical Corporation | Group III nitride semiconductor substrate and method for cleaning the same |
| WO2009073588A1 (en) * | 2007-12-06 | 2009-06-11 | Mallinckrodt Baker, Inc. | Fluoride-containing photoresist stripper or residue removing cleaning compositions containing conjugate oligomeric or polymeric material of alpha-hydroxycarbonyl compound/amine or ammonia reaction |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2008066747A (en) | 2008-03-21 |
| JP2001508239A (en) | 2001-06-19 |
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