WO2001040425A2 - Post chemical-mechanical planarization (cmp) cleaning composition - Google Patents
Post chemical-mechanical planarization (cmp) cleaning composition Download PDFInfo
- Publication number
- WO2001040425A2 WO2001040425A2 PCT/US2000/042197 US0042197W WO0140425A2 WO 2001040425 A2 WO2001040425 A2 WO 2001040425A2 US 0042197 W US0042197 W US 0042197W WO 0140425 A2 WO0140425 A2 WO 0140425A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- cleaning
- solution
- cleaning solution
- gallic acid
- cmp
- Prior art date
Links
- 238000004140 cleaning Methods 0.000 title claims abstract description 147
- 239000000203 mixture Substances 0.000 title claims description 22
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims abstract description 64
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims abstract description 52
- 239000010949 copper Substances 0.000 claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052802 copper Inorganic materials 0.000 claims abstract description 38
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229940074391 gallic acid Drugs 0.000 claims abstract description 32
- 235000004515 gallic acid Nutrition 0.000 claims abstract description 32
- 239000000758 substrate Substances 0.000 claims abstract description 31
- 238000004377 microelectronic Methods 0.000 claims abstract description 18
- 230000007797 corrosion Effects 0.000 claims abstract description 16
- 238000005260 corrosion Methods 0.000 claims abstract description 16
- 229910001868 water Inorganic materials 0.000 claims abstract description 16
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003112 inhibitor Substances 0.000 claims abstract description 11
- 239000000908 ammonium hydroxide Substances 0.000 claims abstract description 9
- 125000001453 quaternary ammonium group Chemical group 0.000 claims abstract description 7
- 150000001412 amines Chemical class 0.000 claims abstract description 6
- 239000008367 deionised water Substances 0.000 claims description 27
- 229910021641 deionized water Inorganic materials 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 25
- 239000012141 concentrate Substances 0.000 claims description 14
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 8
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 claims description 8
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 6
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 6
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 5
- 239000012964 benzotriazole Substances 0.000 claims description 5
- -1 -methylaminoethanol Chemical compound 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229940079877 pyrogallol Drugs 0.000 claims description 4
- JPIGSMKDJQPHJC-UHFFFAOYSA-N 1-(2-aminoethoxy)ethanol Chemical compound CC(O)OCCN JPIGSMKDJQPHJC-UHFFFAOYSA-N 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 claims description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- KVFVBPYVNUCWJX-UHFFFAOYSA-M ethyl(trimethyl)azanium;hydroxide Chemical compound [OH-].CC[N+](C)(C)C KVFVBPYVNUCWJX-UHFFFAOYSA-M 0.000 claims description 3
- 229940087646 methanolamine Drugs 0.000 claims 3
- 238000007865 diluting Methods 0.000 claims 1
- 238000001914 filtration Methods 0.000 claims 1
- XMYQHJDBLRZMLW-UHFFFAOYSA-N methanolamine Chemical compound NCO XMYQHJDBLRZMLW-UHFFFAOYSA-N 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 116
- 239000002002 slurry Substances 0.000 description 23
- 235000012431 wafers Nutrition 0.000 description 23
- 230000008569 process Effects 0.000 description 20
- 239000002245 particle Substances 0.000 description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 15
- 238000012360 testing method Methods 0.000 description 11
- 239000004065 semiconductor Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- 238000005498 polishing Methods 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 239000000470 constituent Substances 0.000 description 5
- 238000011109 contamination Methods 0.000 description 5
- 239000012895 dilution Substances 0.000 description 5
- 238000010790 dilution Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- 230000007717 exclusion Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 2
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- NECRQCBKTGZNMH-UHFFFAOYSA-N 3,5-dimethylhex-1-yn-3-ol Chemical compound CC(C)CC(C)(O)C#C NECRQCBKTGZNMH-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008698 shear stress Effects 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/62—Quaternary ammonium compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—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
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2003—Alcohols; Phenols
- C11D3/2041—Dihydric alcohols
- C11D3/2058—Dihydric alcohols aromatic
-
- 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
- C11D3/2003—Alcohols; Phenols
- C11D3/2065—Polyhydric alcohols
-
- 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
- C11D3/2072—Aldehydes-ketones
-
- 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
- C11D3/28—Heterocyclic compounds containing nitrogen in the ring
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/30—Amines; Substituted amines ; Quaternized amines
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- 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
- C11D7/32—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
-
- 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
-
- 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
-
- C11D2111/22—
Definitions
- the present invention relates generally to the field of post chemical-mechanical polishing (post-CMP) cleaning operations, and more specifically to post-CMP cleaning solutions for copper- containing microelectronic substrates.
- post-CMP post chemical-mechanical polishing
- the present day fabrication of semiconductor devices is a complex, multi-step process.
- the CMP process is now a well established enabling technology used by most advanced semiconductor operations for planarization (or "polisliing") of various substrates for production of devices with design geometries less than 0.35 micron.
- the CMP processes involve holding and rotating a thin, flat substrate of the semiconductor material against a wetted polishing surface under controlled chemical, pressure and temperature conditions.
- a chemical slurry containing a polishing agent, such as alumina or silica, is used as the abrasive material.
- the chemical slurry contains selected chemicals which etch various surfaces of the substrate during processing. The combination of mechanical and chemical removal of material during polishing results in superior planarization of the surface.
- the CMP process leaves contamination on the surfaces of the semiconductor substrate.
- This contamination is comprised of abrasive particles from the polishing slurry which may consist of alumina or silica, with reactive chemicals added to the polishing slurry.
- the contaminant layer may comprise reaction products of the polishing slurry and the polished surfaces. It is necessary to remove the contamination prior to subsequent processing of the semiconductor substrate in order to avoid degradation in device reliability and to avoid the introduction of defects which reduce the manufacturing process yield.
- post- CMP cleaning solutions have been developed to cleanse the substrate surface of CMP residuum. Alkaline solutions based on ammonium hydroxide have been traditionally used in post-CMP cleaning applications.
- Post-CMP cleaning solutions that are traditionally effective on alumina and silica-based CMP processes are not effective on copper-containing surfaces. Copper is easily damaged by these cleaning solutions. In addition, cleaning efficacy with the present post-CMP cleaning solutions has been proven unacceptable.
- the solution preferably contains a volumetric ratio of acetic acid to tetramethyl ammonium hydroxide ranging from about 1 to about 50.
- the disclosed aqueous composition contains preferably 7C to 95 wt % monoethanolamme and a corrosion inhibitor at about 5 wt% such as catechol, pyrogallol or gallic acid.
- the pH of the solution is greater that 8.
- the solution may further contain a corrosion inhibitor such as gallic acid, catechol, or pyrogallol.
- U.S. Patent No. 5,466,389 discloses an aqueous alkaline cleaning solution for cleaning microelectronic substrates.
- the cleaning solution contains a metal ion-free alkaline component such as a quaternary ammonium hydroxide (up to 25 wt%), a nonionic surfactant (up to 5 wt%), and a pH-adjusting component, such as acetic acid, to control the pH within the range of 8 to 10.
- a metal ion-free alkaline component such as a quaternary ammonium hydroxide (up to 25 wt%), a nonionic surfactant (up to 5 wt%), and a pH-adjusting component, such as acetic acid, to control the pH within the range of 8 to 10.
- a post-CMP cleaning composition for copper-containing surfaces.
- Such a post-CMP cleaning composition must effectuate substantial particle removal from the target surface and prevent or substantially lessen corrosion of the copper-containing substrate.
- Such a post-CMP cleaning composition must also refrain from attacking the process equipment used in the post-CMP process.
- Such a post-CMP cleaning composition should also be economical, work effectively through a wide temperature range, and preferably contain chemical components of comparatively lower toxicity.
- Such a post-CMP cleaning composition should also be useful in cleaning operations following CMP processes utilizing alumina or silica-based slurries.
- a cleaning solution for cleaning copper-containing microelectronic substrates comprises a quaternary ammonium hydroxide selected from the group consisting of tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylethylammonium hydroxide, and combinations thereof; an organic amine selected from the group consisting of monoethanolamine, aminoethylethanolamine, -methylaminoethanol, aminoethoxyethanol, diethanolamine, triethanolamine, C j -C 5 alkanolamines, and combinations thereof; a corrosion inhibitor selected from the group consisting of gallic acid, catechol, pyrogallol, resorcinol, hydroquinone, benzotriazole, and combinations thereof; and water.
- the pH of the solution is greater than 10.
- a cleaning solution for cleaning copper-containing microelectronic substrates comprises a) tetramethylammonium hydoxide, b) monoethanclamine, c) gallic acid, and deionized water.
- the pH of the solution is greater than 10.
- tetramethylammonium hvdroxide is in the cleaning solution in an amount in the range from about 0.15 wt% to about 1.25 wt%
- monoethanolamine is in the solution in an amount in the range from about 0.4 wt% to about 2.25 wt%
- gallic acid is in the solution in an amount in the range from about 0.09 wt% to about 0.9 wt%.
- a concentrate composition for a cleaning solution for cleaning copper-containing microelectronic substrates in also provided.
- the concentrate composition comprises tetramethylammonium hydroxide in an amount in the range from about 8.0 wt% to about 12.4 wt%, monoethanolamine in an amount in the range from about 14.4 wt% to about 27.8 wt%, gallic acid in an amount in the range from about 5.6 wt% to about 10.9 wt%, and the balance deionized water.
- a cleaning solution is provided comprising the concentrate in an amount in the range from about 1.5 wt% to about 12.5 wt% in the cleaning solution.
- Figure 1 is a graph illustrating the relationship between particle counts measured from wafers cleaned with a cleaning solution of the invention and process cleaning time.
- a cleaning solution for cleaning copper-containing microelectronic substrates following CMP processing is provided. Cleaning copper-containing substrates following CMP processing is generally referred to as "post-Cu CMP" or “post-CMP copper clean”.
- a "copper-containing microelectronic substrate” is understood herein to refer to a substrate surface manufactured for use in microelectronic, integrated circuit, or computer chip applications, wherein the substrate contains copper-containing components. Copper-containing components may include, for example, metallic interconnects that are predominately copper or copper alloy. It is understood that the microelectronic surface may also be composed of semiconductor materials, such as TiN, Ta, TiW (as copper diffusion barrier metals), and silica. Generally, a copper-containing microelectronic substrate contains about 1-20% Cu, including the copper interconnects.
- the cleaning solution of the invention may find application for any cleaning operation during the fabrication of microelectronic substrates, such as semiconductor wafers. Most notably, such cleaning applications include post- Via formations and post-CMP processes.
- the fabrication of conventional semiconductor wafers entails many steps requiring planarization, followed by the removal of residual product from the planarization process.
- the cleaning solution of the invention comprises a quaternary ammonium hydroxide, an organic amine, a corrosion inhibitor, and the balance water.
- the quaternary ammonium hydroxide is selected from the group consisting of tetramethyl- ammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, trimethylethylammonium hydroxide, and combinations thereof.
- Quaternary ammonium hydroxide is present in the solution in an amount from about 0.15 wt% to about 1.75 wt%.
- the organic amine is selected from the group consisting of monoethanolamine, aminoethylethanolamine, methylaminoethanol, aminoethoxyethanol, diethanolamine, triethanolamine, -C 5 alkanolamines, and combinations thereof.
- Organic amine is present in the solution in an amount from about 0.4 wt% to about 2.75 wt%.
- the corrosion inhibitor is selected from the group consisting of gallic acid, catechol, pyrogallol, resorcinol, hydroquinone, benzotriazole, and combinations thereof.
- Corrosion inhibitor is present in the solution in an amount from about 0.09 wt% to about 1.0 wt%.
- the pH of a cleaning solution of the invention is greater than 10.
- the cleaning solution comprises tetramethylammonium hydroxide ("TMAH”), monoethanolamine (“ME A”), gallic acid, and water.
- TMAH tetramethylammonium hydroxide
- ME A monoethanolamine
- gallic acid is present in the solution in an amount in the range from about 0.09 wt% to about 0.9 wt%; and the balance water.
- the constituents of the cleaning solution of the invention may be mixed together in any order.
- the order of addition is exemplified with respect to the preferred embodiment containing TMAH, MEA, gallic acid, and water.
- 50% of the water in the final solution is added to all of the MEA, followed by addition of the gallic acid.
- the remaining 50% of water is added when the gallic acid is dissolved.
- the TMAH is then added and the composition mixed under low shear-stress conditions for about 10 minutes.
- the resulting mixture is then filtered through a 0.1 micron filter.
- a cleaning solution of the invention is that the non-aqueous constituents (the constituents other than water) are present in the solution in comparatively smaller quantities than prior art cleaning solutions.
- a cleaning solution of the invention is therefore more "dilute" than prior art post-CMP cleaning solutions. This is an economic advantage since an effective cleaning solution can be formulated more cheaply, which is of importance since such post-CMP cleaning solutions are used in large quantities.
- a concentrated composition is provided that may be diluted to be used as a cleaning solution.
- a concentrated composition of the invention, or "concentrate” advantageously permits a CMP process engineer, for example, to dilute the concentrate to the desired strength and pH.
- a concentrate also permits longer shelf life, and easier shipping and storage of the product.
- a concentrate of the invention preferably comprises
- TMAH in an amount in the range from about 8.0 to about 12.4 wt%
- MEA in an amount in the range from about 14.4 to about 27.8 wt%
- gallic acid in an amount in the range from about 5.6 to about 10.9 wt%
- the balance water preferably deionized water
- a concentrate of the invention is preferably diluted for use in post-CMP cleaning applications by adding deionized water until the concentrate is from about 1.5 wt% to about 12.5 wt% of the prepared cleaning solution.
- the cleaning solution of the invention may be employed for cleaning microelectronic substrates at temperatures ranging from ambient conditions to about 70°C. It is generally recognized that cleaning improves as temperature increases. At temperatures greater than about 70°C, evaporation of constituent cleaning solution species risks adversely altering the chemistry of the cleaning system over time in a process open to ambient conditions.
- the cleaning solution of the invention has a pH greater than 10. More preferably, the pH of a cleaning solution of the invention is maintained in the range from about 11.0 to about 12.2. A pH greater than 10 is necessary to obtain a negative zeta potential on the surface of the substrate and the remaining particulates during the cleaning operation.
- the cleaning solution of the invention meets generally accepted industry cleaning performance standards for post-CMP applications.
- a common industrial cleaning target is a particle count on the substrate wafer of less than 20 particles greater than 0.2 microns in size for a 200mm wafer, with a 5mm edge exclusion.
- the cleaning solution of the invention limits copper corrosion to smoothing of the surface and does not damage processing equipment.
- the cleaning solution of the invention may be used with a large variety of conventional cleaning tools, including Verteq single wafer megasonic Goldfinger, OnTrak systems, DDS (double-sided scrubbers) and Megasonic batch wet bench systems.
- the cleaning solution of the invention may be used successfully on surfaces containing copper, tungsten, and/or silica.
- Via cleaning is one application of the cleaning solution of the invention.
- Vias are holes etched in microelectronic substrates to provide a conduit for connecting metal layers. Etching the substrate surface with a gaseous etchant forms Vias.
- the substrate is commonly a dielectric material, such as Fluorinated Silica Glass (FSG).
- FSG Fluorinated Silica Glass
- the residue remaining on the substrate surface and Via walls must be removed following the etching process.
- the residue is often referred to as "side wall polymer", as it is also found on the vertical walls of the Via.
- Etching residue may also be located at the bottom of the Via. on top of the metal.
- the cleaning solution of the invention does not react with or affect the exposed dielectric material.
- Example 1 The performance of a post-Cu CMP cleaning solution of the invention was compared to the performance of prior art, commercially available post-Cu CMP cleaning solutions.
- Sample 200 mm TEOS wafers (non-copper containing) were pre-cleaned using a scrubber. Defects were measured on a Tencor 64C : all wafers had ⁇ 100 defects at 0.2 ⁇ m.
- Three separate series of performance tests were conducted using a different commerciallv-available CMP slurry composition to contaminate the wafers: series I: Cabot 5001 (as first step slurry) series II: Cabot 4200 (as second step slurry) series III: Cabot SS25 (an oxide slurry) Each of the three slurries are available from Cabot
- the Cabot 5001 and 4200 slurries were prepared with the recommended amount of hydrogen peroxide per labeling instructions. Tests were conducted within 24 hours of the slurry's preparation.
- the sample wafers were first immersed into a solution of deionized water and surfactant (Wako NCW-601 A), then 500 ml of CMP slurry.
- the wafers were individually dipped in the slurry for 10 sec, dipped again in the water/surfactant solution, then processed through an SRD (Spin Rinse Dry cycle) at 1300 rpm to 5 min., without heat, to dry the wafers.
- SRD Spin Rinse Dry cycle
- Post-CMP cleaning solutions were prepared as follows: Solution A: Cabot 101 (Cabot Corp.) Solution B: EKC CMPC5000 (EKC Corp.), 20:1 dilution
- Solution D deionized water, ammonium hydroxide (100:1 dilution), and a surfactant (ammonium peroxide/acetic acid)
- Solution E TMAH 0.5 wt%
- Solution E Solution E, further containing 0.2 wt% of a surfactant (Surfynol 420; Air Products)
- the post-CMP cleaning solutions were evaluated for slurry removal using a process time of 38 sec. on a Goldfinger GFS- CMP-200C module without rotation. Megasonic agitation was employed. Static tests measure the strength of cleaning ability unaided by any other mechanical energy.
- a "clean angle” is the angle formed by the delineated appearance of a clean wafer on both sides of the megasonic wand; the greater the measured clean angle, the more effective is the cleaning solution.
- Example 2 The post-CMP cleaning solutions (A-F) of Example I were evaluated in a static test as in Example 1, except that the sample wafers were dipped in all three CMP slurries (series I, II and III) consecutively, then dipped into one of the cleaning solutions A-F.
- Example 3 The multiple slurry contamination test of Example 2 was again conducted, but under dynamic cleaning conditions. That is, the subject wafer was rotated at 200 rpm during cleaning solution application (and mega-sonic agitation) on the Goldfinger GFS-CMP- 200C. Particle counts were measured using the Tencor 6400.
- Tests were conducted to evaluate the relative cleaning performance of post-CMP cleaning solutions of varying composition.
- Cleaning solutions were prepared by mixing deionized water TMAH, gallic acid, and one of three amine compounds (MEA, hydroxylamine, or N-monoethanolamine).
- TMAH deionized water
- MEA hydroxylamine
- N-monoethanolamine amine compounds
- Solution K was 1.7 wt% NH 4 OH in deionized water and Solution L was 1:2:10 NH 4 OH:H 2 0 2 :H 2 0. The pH of each cleaning solution was measured.
- W-CMP slurry (1:1 dilution of Ultraplane-MC W CMP base and deionized water). Each slide was then dipped into 250 ml deionized water, then into the subject cleaning solution. Each slide was then dipped into 100 ml deionized water, then dipped into another separate deionized water bath. The slides were hung to air dry under ambient conditions. Between each test, all deionized water baths were replaced. Dried slides were visually evaluated for evidence of remaining CMP slurry, as evidenced by the degree of cloudiness observed on the slide. The dried slides were compared and ranked from best to worst.
- Example 4 were evaluated for the tendency to corrode copper.
- Copper strips were weighed, then placed in 200 ml of the subject cleaning solution for 20 hours under ambient conditions. The copper strips were thereafter removed from the cleaning solution, rinsed with deionized water, and dried. The cleaning solution was visually inspected for color change. The copper strips were visually inspected for color changes and weighed. Color changes are evidence of corrosion.
- a series of cleaning solutions were prepared to evaluate the relationship between TMAH, MEA, and gallic acid in aqueous cleaning solutions.
- Cleaning solutions were prepared by combining TMAH, MEA, gallic acid, and deionized water such that the concentration of TMAH was either 0.75 wt%, 0.5 wt%, or 0.25 wt%; the concentration of MEA was either 1.8 wt%, 0.9 wt%, or 0 wt% the concentration of gallic acid was either 0.7 wt%, 0.35 wt%, or 0 wt%; and the balance deionized water in each case.
- Nine -test solutions were prepared as set forth in Table VI.
- the prepared cleaning solutions were evaluated for cleaning performance according to the glass slide dip test procedure set forth in Example 4.
- the prepared cleaning solutions were also evaluated for tendency to corrode copper according to the copper strip test procedure of Example 5.
- solutions that performed best as cleaning agents in the dip test contained TMAH, MEA, and gallic acid. Solutions not containing at least one of these constituents did not perform as well. The results suggest a synergistic cleaning effect is present when TMAH, MEA, and gallic acid co-exist in a cleaning solution, particularly in the preferred amounts.
- Sample wafers were then cleaned on a Verteq Goldfinger apparatus using a cleaning solution of the invention (20: 1 dilution in deionized water of a concentrate prepared from 10% TMAH, 18% MEA, 7% gallic acid, and the balance deionized water). Sample wafers were cleaned for time periods of 25 sec, 45 sec, or 65 sec. After cleaning, particle counts (particles > 0.2 micron) were acquired. All particle counts were determined on a Tencor 6420 particle counter at 5 mm and 8 mm edge exclusions (EE).
- a cleaning solution of the invention (20: 1 dilution in deionized water of a concentrate prepared from 10% TMAH, 18% MEA, 7% gallic acid, and the balance deionized water). Sample wafers were cleaned for time periods of 25 sec, 45 sec, or 65 sec. After cleaning, particle counts (particles > 0.2 micron) were acquired. All particle counts were determined on a Tencor 6420 particle counter at 5 mm and 8 mm edge exclusions
- the cleaning solutions of the present invention when used on copper wafers, have a tendency to etch the copper surface by a corrosion process. This mild attack on the surface may be beneficial in that it greatly promotes the removal of unwanted particles.
- the cleaning solution may be modified to reduce or eliminate corrosion by one or both of the following:
Abstract
A cleaning solution is provided for cleaning copper-containing microelectronic substrates, particularly for post-CMP or Via formation cleaning. The cleaning solution comprises a quaternary ammonium hydroxide, an organic amine, a corrosion inhibitor, and water. A preferred cleaning solution comprises tetramethylammonium hydroxide, monoethanolamine, gallic acid, and water. The pH of the cleaning solution is greater than 10.
Description
POST CHEMICAL-MECHANICAL PLANARIZATION (CMP) CLEANING COMPOSITION
Field of the Invention
The present invention relates generally to the field of post chemical-mechanical polishing (post-CMP) cleaning operations, and more specifically to post-CMP cleaning solutions for copper- containing microelectronic substrates.
Background of the Invention
The present day fabrication of semiconductor devices is a complex, multi-step process. The CMP process is now a well established enabling technology used by most advanced semiconductor operations for planarization (or "polisliing") of various substrates for production of devices with design geometries less than 0.35 micron.
The CMP processes involve holding and rotating a thin, flat substrate of the semiconductor material against a wetted polishing
surface under controlled chemical, pressure and temperature conditions. A chemical slurry containing a polishing agent, such as alumina or silica, is used as the abrasive material. In addition, the chemical slurry contains selected chemicals which etch various surfaces of the substrate during processing. The combination of mechanical and chemical removal of material during polishing results in superior planarization of the surface.
The CMP process, however, leaves contamination on the surfaces of the semiconductor substrate. This contamination is comprised of abrasive particles from the polishing slurry which may consist of alumina or silica, with reactive chemicals added to the polishing slurry. In addition, the contaminant layer may comprise reaction products of the polishing slurry and the polished surfaces. It is necessary to remove the contamination prior to subsequent processing of the semiconductor substrate in order to avoid degradation in device reliability and to avoid the introduction of defects which reduce the manufacturing process yield. Thus, post- CMP cleaning solutions have been developed to cleanse the substrate surface of CMP residuum. Alkaline solutions based on ammonium hydroxide have been traditionally used in post-CMP cleaning applications. To date, most CMP applications have been directed to aluminum, tungsten, tantalum, and oxide-containing surfaces.
However, copper is increasingly becoming a material of choice in the production of interconnects in semiconductor fabrication. Copper is replacing aluminum as the metal of choice in such fabrication. Conventional post-CMP processes are inadequate for cleaning surfaces containing copper. Copper, copper oxide, and the slurry particles are the contaminants that exist on the copper- containing surface following this CMP process. The copper surface contamination diffuses quickly in silicon and silicon dioxide, and therefore, it must be removed from all wafer surfaces to prevent device failure.
Post-CMP cleaning solutions that are traditionally effective on alumina and silica-based CMP processes are not effective on copper-containing surfaces. Copper is easily damaged by these cleaning solutions. In addition, cleaning efficacy with the present post-CMP cleaning solutions has been proven unacceptable.
Nam, U.S. Patent No. 5,863,344, discloses a cleaning solution for semiconductor devices containing tetramethyl ammonium hydroxide, acetic acid, and water. The solution preferably contains a volumetric ratio of acetic acid to tetramethyl ammonium hydroxide ranging from about 1 to about 50.
Ward, U.S. Patent No. 5,597,420, discloses an aqueous stripping composition useful for cleaning organic and inorganic compounds from a substrate that will not corrode or dissolve metal circuitry in the substrate. The disclosed aqueous composition
contains preferably 7C to 95 wt % monoethanolamme and a corrosion inhibitor at about 5 wt% such as catechol, pyrogallol or gallic acid.
Ward, U.S. Patent No. 5,709,756, discloses a cleaning composition containing about 25 to 48 wt% hydroxylamine, 1 to 20 wt% ammonium fluoride, and water. The pH of the solution is greater that 8. The solution may further contain a corrosion inhibitor such as gallic acid, catechol, or pyrogallol.
Ilardi et al.. U.S. Patent No. 5,466,389, discloses an aqueous alkaline cleaning solution for cleaning microelectronic substrates. The cleaning solution contains a metal ion-free alkaline component such as a quaternary ammonium hydroxide (up to 25 wt%), a nonionic surfactant (up to 5 wt%), and a pH-adjusting component, such as acetic acid, to control the pH within the range of 8 to 10.
There is a need for a post-CMP cleaning composition for copper-containing surfaces. Such a post-CMP cleaning composition must effectuate substantial particle removal from the target surface and prevent or substantially lessen corrosion of the copper-containing substrate. Such a post-CMP cleaning composition must also refrain from attacking the process equipment used in the post-CMP process. Such a post-CMP cleaning composition should also be economical, work effectively through a wide temperature range, and preferably contain chemical components of comparatively lower toxicity. Such
a post-CMP cleaning composition should also be useful in cleaning operations following CMP processes utilizing alumina or silica-based slurries.
Summary of the Invention A cleaning solution for cleaning copper-containing microelectronic substrates comprises a quaternary ammonium hydroxide selected from the group consisting of tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylethylammonium hydroxide, and combinations thereof; an organic amine selected from the group consisting of monoethanolamine, aminoethylethanolamine, -methylaminoethanol, aminoethoxyethanol, diethanolamine, triethanolamine, Cj-C5 alkanolamines, and combinations thereof; a corrosion inhibitor selected from the group consisting of gallic acid, catechol, pyrogallol, resorcinol, hydroquinone, benzotriazole, and combinations thereof; and water. The pH of the solution is greater than 10.
A cleaning solution for cleaning copper-containing microelectronic substrates comprises a) tetramethylammonium hydoxide, b) monoethanclamine, c) gallic acid, and deionized water. The pH of the solution is greater than 10. Preferably, tetramethylammonium hvdroxide is in the cleaning solution in an
amount in the range from about 0.15 wt% to about 1.25 wt%, monoethanolamine is in the solution in an amount in the range from about 0.4 wt% to about 2.25 wt%, and gallic acid is in the solution in an amount in the range from about 0.09 wt% to about 0.9 wt%. A concentrate composition for a cleaning solution for cleaning copper-containing microelectronic substrates in also provided. The concentrate composition comprises tetramethylammonium hydroxide in an amount in the range from about 8.0 wt% to about 12.4 wt%, monoethanolamine in an amount in the range from about 14.4 wt% to about 27.8 wt%, gallic acid in an amount in the range from about 5.6 wt% to about 10.9 wt%, and the balance deionized water. A cleaning solution is provided comprising the concentrate in an amount in the range from about 1.5 wt% to about 12.5 wt% in the cleaning solution.
Brief Description of the Figures
Figure 1 is a graph illustrating the relationship between particle counts measured from wafers cleaned with a cleaning solution of the invention and process cleaning time.
Detailed Description of the Invention
A cleaning solution for cleaning copper-containing microelectronic substrates following CMP processing is provided.
Cleaning copper-containing substrates following CMP processing is generally referred to as "post-Cu CMP" or "post-CMP copper clean". A "copper-containing microelectronic substrate" is understood herein to refer to a substrate surface manufactured for use in microelectronic, integrated circuit, or computer chip applications, wherein the substrate contains copper-containing components. Copper-containing components may include, for example, metallic interconnects that are predominately copper or copper alloy. It is understood that the microelectronic surface may also be composed of semiconductor materials, such as TiN, Ta, TiW (as copper diffusion barrier metals), and silica. Generally, a copper-containing microelectronic substrate contains about 1-20% Cu, including the copper interconnects.
The cleaning solution of the invention may find application for any cleaning operation during the fabrication of microelectronic substrates, such as semiconductor wafers. Most notably, such cleaning applications include post- Via formations and post-CMP processes. The fabrication of conventional semiconductor wafers entails many steps requiring planarization, followed by the removal of residual product from the planarization process.
The cleaning solution of the invention comprises a quaternary ammonium hydroxide, an organic amine, a corrosion inhibitor, and the balance water. The quaternary ammonium hydroxide is selected from the group consisting of tetramethyl-
ammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, trimethylethylammonium hydroxide, and combinations thereof. Quaternary ammonium hydroxide is present in the solution in an amount from about 0.15 wt% to about 1.75 wt%.
The organic amine is selected from the group consisting of monoethanolamine, aminoethylethanolamine, methylaminoethanol, aminoethoxyethanol, diethanolamine, triethanolamine, -C5 alkanolamines, and combinations thereof. Organic amine is present in the solution in an amount from about 0.4 wt% to about 2.75 wt%.
The corrosion inhibitor is selected from the group consisting of gallic acid, catechol, pyrogallol, resorcinol, hydroquinone, benzotriazole, and combinations thereof. Corrosion inhibitor is present in the solution in an amount from about 0.09 wt% to about 1.0 wt%.
The pH of a cleaning solution of the invention is greater than 10.
In a preferred embodiment of the cleaning solution of the invention, the cleaning solution comprises tetramethylammonium hydroxide ("TMAH"), monoethanolamine ("ME A"), gallic acid, and water. Most preferably, TMAH is present in the solution in an amount in the range from about 0.15 wt% to about 1.25 wt%; ME A is present in the solution in an amount in the
range from about 0.4 wt% to about 2.25 wt%; gallic acid is present in the solution in an amount in the range from about 0.09 wt% to about 0.9 wt%; and the balance water.
The constituents of the cleaning solution of the invention may be mixed together in any order. The order of addition is exemplified with respect to the preferred embodiment containing TMAH, MEA, gallic acid, and water. In a preferred method of preparation, 50% of the water in the final solution is added to all of the MEA, followed by addition of the gallic acid. The remaining 50% of water is added when the gallic acid is dissolved. The TMAH is then added and the composition mixed under low shear-stress conditions for about 10 minutes. The resulting mixture is then filtered through a 0.1 micron filter.
The components of the preferred embodiment cleaning solution of the invention are commercially available.
An important feature of the cleaning solution of the invention is that the non-aqueous constituents (the constituents other than water) are present in the solution in comparatively smaller quantities than prior art cleaning solutions. A cleaning solution of the invention is therefore more "dilute" than prior art post-CMP cleaning solutions. This is an economic advantage since an effective cleaning solution can be formulated more cheaply, which is of importance since such post-CMP cleaning solutions are used in large quantities.
In an alternative embodiment of the invention, a concentrated composition is provided that may be diluted to be used as a cleaning solution. A concentrated composition of the invention, or "concentrate", advantageously permits a CMP process engineer, for example, to dilute the concentrate to the desired strength and pH. A concentrate also permits longer shelf life, and easier shipping and storage of the product.
A concentrate of the invention preferably comprises
TMAH in an amount in the range from about 8.0 to about 12.4 wt%, MEA in an amount in the range from about 14.4 to about 27.8 wt%, gallic acid in an amount in the range from about 5.6 to about 10.9 wt%, and the balance water (preferably deionized water).
A concentrate of the invention is preferably diluted for use in post-CMP cleaning applications by adding deionized water until the concentrate is from about 1.5 wt% to about 12.5 wt% of the prepared cleaning solution.
The cleaning solution of the invention may be employed for cleaning microelectronic substrates at temperatures ranging from ambient conditions to about 70°C. It is generally recognized that cleaning improves as temperature increases. At temperatures greater than about 70°C, evaporation of constituent cleaning solution species risks adversely altering the chemistry of the cleaning system over time in a process open to ambient conditions.
The cleaning solution of the invention, as noted, has a pH greater than 10. More preferably, the pH of a cleaning solution of the invention is maintained in the range from about 11.0 to about 12.2. A pH greater than 10 is necessary to obtain a negative zeta potential on the surface of the substrate and the remaining particulates during the cleaning operation.
The cleaning solution of the invention meets generally accepted industry cleaning performance standards for post-CMP applications. A common industrial cleaning target is a particle count on the substrate wafer of less than 20 particles greater than 0.2 microns in size for a 200mm wafer, with a 5mm edge exclusion.
The cleaning solution of the invention limits copper corrosion to smoothing of the surface and does not damage processing equipment. The cleaning solution of the invention may be used with a large variety of conventional cleaning tools, including Verteq single wafer megasonic Goldfinger, OnTrak systems, DDS (double-sided scrubbers) and Megasonic batch wet bench systems.
The cleaning solution of the invention may be used successfully on surfaces containing copper, tungsten, and/or silica.
Via cleaning is one application of the cleaning solution of the invention. Vias are holes etched in microelectronic substrates to provide a conduit for connecting metal layers. Etching the substrate surface with a gaseous etchant forms Vias. The substrate is
commonly a dielectric material, such as Fluorinated Silica Glass (FSG). The residue remaining on the substrate surface and Via walls must be removed following the etching process. The residue is often referred to as "side wall polymer", as it is also found on the vertical walls of the Via. Etching residue may also be located at the bottom of the Via. on top of the metal. The cleaning solution of the invention does not react with or affect the exposed dielectric material.
The following Examples are merely illustrative of the invention and are not intended to be limiting.
Example 1 The performance of a post-Cu CMP cleaning solution of the invention was compared to the performance of prior art, commercially available post-Cu CMP cleaning solutions. Sample 200 mm TEOS wafers (non-copper containing) were pre-cleaned using a scrubber. Defects were measured on a Tencor 64C : all wafers had < 100 defects at 0.2 μm. Three separate series of performance tests were conducted using a different commerciallv-available CMP slurry composition to contaminate the wafers: series I: Cabot 5001 (as first step slurry) series II: Cabot 4200 (as second step slurry) series III: Cabot SS25 (an oxide slurry)
Each of the three slurries are available from Cabot
Corporation (Boston, Massachusetts). The Cabot 5001 and 4200 slurries were prepared with the recommended amount of hydrogen peroxide per labeling instructions. Tests were conducted within 24 hours of the slurry's preparation.
The sample wafers were first immersed into a solution of deionized water and surfactant (Wako NCW-601 A), then 500 ml of CMP slurry. The wafers were individually dipped in the slurry for 10 sec, dipped again in the water/surfactant solution, then processed through an SRD (Spin Rinse Dry cycle) at 1300 rpm to 5 min., without heat, to dry the wafers.
Post-CMP cleaning solutions were prepared as follows: Solution A: Cabot 101 (Cabot Corp.) Solution B: EKC CMPC5000 (EKC Corp.), 20:1 dilution
Solution C: buffered oxalic acid, pH = 5.35 Solution D: deionized water, ammonium hydroxide (100:1 dilution), and a surfactant (ammonium peroxide/acetic acid) Solution E: TMAH 0.5 wt%
MEA 0.9 wt% gallic acid 0.35 wt% deionized water 98.25 wt% (pH = 12.3- 12.6)
Solution F: Solution E, further containing 0.2 wt% of a surfactant (Surfynol 420; Air Products)
The post-CMP cleaning solutions were evaluated for slurry removal using a process time of 38 sec. on a Goldfinger GFS- CMP-200C module without rotation. Megasonic agitation was employed. Static tests measure the strength of cleaning ability unaided by any other mechanical energy.
The wafers were then scanned at 0.2 μm using a Tencor 6400 and a clean angle was measured. A "clean angle" is the angle formed by the delineated appearance of a clean wafer on both sides of the megasonic wand; the greater the measured clean angle, the more effective is the cleaning solution.
The results are shown in Table I.
The results indicate that a post-Cu CMP cleaning solution of the invention (solution E) performed better during static wafer tests than post-CMP cleaning solutions of the prior art. The performance of solution E in removing CMP residuum was demonstrably more significant in series II and series III, as evidenced by clean angles measured at greater than 100 degrees. It should be noted that one skilled in the art would recognize that measured clean angles differing in only several degrees represent a significant difference in performance. The results also indicate that the inclusion oftertain surfactant in a cleaning solution of the invention (solution • F) does not enhance the performance of the cleaning solution in a static test.
Example 2 The post-CMP cleaning solutions (A-F) of Example I were evaluated in a static test as in Example 1, except that the sample wafers were dipped in all three CMP slurries (series I, II and III) consecutively, then dipped into one of the cleaning solutions A-F.
The results are shown in Table II.
The results indicate that a post-CMP cleaning solution of the invention (solution E) performed better than cleaning solutions of the prior an, as evidenced by the greater cleaning angle measured.
Example 3 The multiple slurry contamination test of Example 2 was again conducted, but under dynamic cleaning conditions. That is, the subject wafer was rotated at 200 rpm during cleaning solution application (and mega-sonic agitation) on the Goldfinger GFS-CMP- 200C. Particle counts were measured using the Tencor 6400.
The results are shown in Table III.
The results indicate that a post-CMP cleaning solution of the invention performed significantly better than cleaning solutions of the prior art, as evidenced by the lower particle counts achieved at a 190 sec. process time.
Example 4
Tests were conducted to evaluate the relative cleaning performance of post-CMP cleaning solutions of varying composition.
Cleaning solutions were prepared by mixing deionized water TMAH, gallic acid, and one of three amine compounds (MEA, hydroxylamine, or N-monoethanolamine). The composition of the prepared cleaning solutions is set forth in Table IV. For purposes of comparison, two additional cleaning solutions were prepared:
Solution K was 1.7 wt% NH4OH in deionized water and Solution L was 1:2:10 NH4OH:H202:H20. The pH of each cleaning solution was measured.
"Dip tests" were conducted using precleaned Fisher 12-
550-10 glass microscope slides. In the following procedures, all dips were undertaken for 5 sec, and handled with plastic forceps. A sample slide was first dipped into a CMP oxide slurry (Ultraplane P-
1500), then dipped into 250 ml of deionized water, and then into a
W-CMP slurry (1:1 dilution of Ultraplane-MC W CMP base and deionized water). Each slide was then dipped into 250 ml deionized water, then into the subject cleaning solution. Each slide was then dipped into 100 ml deionized water, then dipped into another separate deionized water bath. The slides were hung to air dry under ambient conditions. Between each test, all deionized water baths were replaced.
Dried slides were visually evaluated for evidence of remaining CMP slurry, as evidenced by the degree of cloudiness observed on the slide. The dried slides were compared and ranked from best to worst.
The results are shown in Table IV.
The results indicate that preferred embodiments of the invention performed best (solutions A and B). All solutions of the invention performed better then cleaning solutions of the prior art (solutions K and L).
Example 5
The cleaning solutions prepared in accordance with
Example 4 were evaluated for the tendency to corrode copper.
Copper strips were weighed, then placed in 200 ml of the subject cleaning solution for 20 hours under ambient conditions. The copper strips were thereafter removed from the cleaning solution, rinsed with deionized water, and dried. The cleaning solution was visually inspected for color change. The copper strips were visually inspected for color changes and weighed. Color changes are evidence of corrosion.
The results are set forth in Table V.
The results indicate that preferred embodiments of the invention (solutions A and Bi performed very well. Some of the solutions of the invention caused the copper strip to darken, probably due to the length of the test period (20 hours).
Example 6
A series of cleaning solutions were prepared to evaluate the relationship between TMAH, MEA, and gallic acid in aqueous cleaning solutions. Cleaning solutions were prepared by combining TMAH, MEA, gallic acid, and deionized water such that the concentration of TMAH was either 0.75 wt%, 0.5 wt%, or 0.25 wt%;
the concentration of MEA was either 1.8 wt%, 0.9 wt%, or 0 wt% the concentration of gallic acid was either 0.7 wt%, 0.35 wt%, or 0 wt%; and the balance deionized water in each case. Nine -test solutions were prepared as set forth in Table VI. The prepared cleaning solutions were evaluated for cleaning performance according to the glass slide dip test procedure set forth in Example 4. The prepared cleaning solutions were also evaluated for tendency to corrode copper according to the copper strip test procedure of Example 5.
The results are shown in Table VI.
The results indicate that the solutions that performed best as cleaning agents in the dip test (solutions 4 and 8) contained TMAH, MEA, and gallic acid. Solutions not containing at least one of these constituents did not perform as well. The results suggest a synergistic cleaning effect is present when TMAH, MEA, and gallic acid co-exist in a cleaning solution, particularly in the preferred amounts.
Example 7
The effectiveness of a TM AH/ME A/gallic acid cleaning solution of the invention was evaluated. PTEOS wafers (300 mm) were measured for particle counts (particles > 0.2 micron), prior to
CMP treatment. The wafers were then polished for 45 seconds using
Cabot EPC4200 slurry on a Strasbaugh Symphony CMP tool.
Sample wafers were then cleaned on a Verteq Goldfinger apparatus using a cleaning solution of the invention (20: 1 dilution in deionized water of a concentrate prepared from 10% TMAH, 18% MEA, 7% gallic acid, and the balance deionized water). Sample wafers were cleaned for time periods of 25 sec, 45 sec, or 65 sec. After cleaning, particle counts (particles > 0.2 micron) were acquired. All particle counts were determined on a Tencor 6420 particle counter at 5 mm and 8 mm edge exclusions (EE).
The results are shown in Figure 1. Particle counts are reported for "pre" CMP/cleaning operations and for "post" CMP/cleaning operations. The results indicate that particle counts,
by virtue of the cleaning process using a cleaning solution of the invention, were lowered below "pre" CMP/cleaning levels.
In certain applications, the cleaning solutions of the present invention, when used on copper wafers, have a tendency to etch the copper surface by a corrosion process. This mild attack on the surface may be beneficial in that it greatly promotes the removal of unwanted particles.
For those applications where slight corrosion of the copper surface is to be avoided, the cleaning solution may be modified to reduce or eliminate corrosion by one or both of the following:
(a) dilution of the cleaning solution with deionized water so that the concentrate is present at about 1.5 wt% in the cleaning solution. (b) using corrosion inhibitor gallic acid in combination with corrosion inhibitor benzotriazole; this combination of inhibitors works synergistically, and lower than ordinary concentrations are effective. It is further understood that the present invention is not limited to the particular embodiments shown and described herein, but that various changes and modifications may be made without departing from the scope and spirit of the invention.
Claims
1. A post-CMP cleaning solution for cleaning microelectronic substrates, the cleaning solution comprising:
0.15 to 1.75% by weight of a quaternary ammonium hydroxide selected from the group consisting of tetramethylammonium hydroxide, tetramethylammonium hydroxide, trimethylethylammonium hydroxide, and combinations thereof;
0.4 to 2.75% by weight of an organic amine selected from the group consisting of monoethanolamine, aminoethylethanolamine, -methylaminoethanol, aminoethoxyethanol, diethanolamine, triethanolamine, O-Cs alkanolamines, and combinations thereof;
0.09 to 1.0% by weight of a corrosion inhibitor selected from the group consisting of gallic acid, catechol, pyrogallol, resorcinol, hydroquinone, benzotriazole, and combinations thereof; balance deionized water; wherein the pH of the solution is greater than 10.
2. A post-CMP cleaning solution for cleaning microelectronic substrates, the cleaning solution comprising: a. 0.15 to 1.25% by weight tetramethylammonium hydroxide; b. 0.4 to 2.25% by weight monoethanolamine; c. 0.09 to 0.9% by weight gallic acid; d. balance deionized water, wherein the pH of the solution is greater than 10.
3. The cleaning solution of claim 2, wherein the tetramethylammonium hydroxide is present in an amount in the range from about 0.15 wt% to about 1.25 wt%. 4. The cleaning solution of claim 2, wherein the monoethanolamine is present in the solution in an amount in the range from about 0.
4 wt% to about 2.25 wt% .
5. The cleaning solution of claim 2, wherein the gallic acid is present in the solution in an amount in the range from about 0.09 wt% to about 0.9 wt% .
6. The cleamng solution of claim 2, wherein tetramethylammonium hydroxide is present in an amount in the range from about 0.15 wt% to about 1.25 wt%; monoethanolamine is present in the solution in an amount in the range from about 0.4 wt% to about 2.25 wt% ; and gallic acid is present in the solution in an amount in the range from about 0.09 wt% to about 0.9 wt% .
7. The cleaning solution of claim 2, wherein the pH of the solution is in the range from about 11.0 to about 12.2.
8. The cleaning solution of claim 1 wherein said corrosion inhibitor is comprised of a combination of gallic acid and benzotriazole. 9. A post-CMP cleaning solution for cleaning microelectronic substrates, comprising:
1.5 to 12.5 wt% of a concentrate consisting essentially of tetramethylammonium hydroxide, in an amount in the range from about 8.0 wt% to about 12.4 wt% ; monoethanolamine, in an amount in the range from about 14.4 wt% to about 27.8 wt % ; gallic acid, in an amount in the range from about 5.6 wt% to about 10.
9 wt% ; balance deionized water and; 87.5 to 98.5 wt% deionized water.
10. A cleaning solution for cleaning copper-containing microelectronic substrates, the cleaning solution prepared by diluting the concentrate of claim 9 with deionized water, wherein the concentrate is in the range from about 1.5 wt% to about 12.5 wt% in the cleaning solution.
11. A method for preparing a post-CMP cleaning solution containing
0.15 to 1.25 wt% tetramethylammonium hydroxide, 0.4 to 2.25 % by weight monoethanolamine, 0.09 to 0.9% by weight gallic acid, balance deionized water comprising the steps of: a) preparing a mixture of one-half of the total final concentration of
water and said monoethanolamine; b) adding said gallic acid to said water and methanolamine mixture; c) adding the balance of the water to said gallic acid-water- methanolamine mixture and mixing with said gallic acid is described; d) adding said tetramethylammonium hydroxide to said water-gallic acid-methanolamine mixture and mixing with low shear conditions to achieve a final mixture; and e) filtering said final mixture through a 0.1 micron filter.
12. A method according to claim 11 , including conducting said mixing step for at least about ten minutes.
13. A method according to claim 11, including the step of adjusting pH of said cleaning solution to greater than 11.
14. A post-CMP cleaning solution according to claim 1, wherein said pH is greater than 11.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/440,917 | 1999-11-16 | ||
US09/440,917 US6194366B1 (en) | 1999-11-16 | 1999-11-16 | Post chemical-mechanical planarization (CMP) cleaning composition |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2001040425A2 true WO2001040425A2 (en) | 2001-06-07 |
WO2001040425A3 WO2001040425A3 (en) | 2002-01-03 |
Family
ID=23750724
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2000/042197 WO2001040425A2 (en) | 1999-11-16 | 2000-11-16 | Post chemical-mechanical planarization (cmp) cleaning composition |
Country Status (2)
Country | Link |
---|---|
US (1) | US6194366B1 (en) |
WO (1) | WO2001040425A2 (en) |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2002065538A2 (en) * | 2001-02-12 | 2002-08-22 | Esc, Inc. | Post chemical-mechanical planarization (cmp) cleaning composition |
WO2003006598A1 (en) * | 2001-07-09 | 2003-01-23 | Mallinckrodt Baker Inc. | Ammonia-free alkaline microelectronic cleaning compositions with improved substrate compatibility |
WO2005066325A2 (en) * | 2003-12-31 | 2005-07-21 | Ekc Technology, Inc. | Cleaner compositions containing free radical quenchers |
US7247208B2 (en) | 2001-07-09 | 2007-07-24 | Mallinckrodt Baker, Inc. | Microelectronic cleaning compositions containing ammonia-free fluoride salts |
US7393819B2 (en) | 2002-07-08 | 2008-07-01 | Mallinckrodt Baker, Inc. | Ammonia-free alkaline microelectronic cleaning compositions with improved substrate compatibility |
US8012973B2 (en) | 2005-10-14 | 2011-09-06 | Proyecto De Biomedicina Cima S.L. | Compounds for the treatment of auricular fibrillation |
WO2016011331A1 (en) * | 2014-07-18 | 2016-01-21 | Cabot Microelectronics Corporation | Cleaning composition following cmp and methods related thereto |
CN107208005A (en) * | 2015-01-13 | 2017-09-26 | 嘉柏微电子材料股份公司 | Cleasing compositions and method for the clean semiconductor chip after chemically mechanical polishing |
Families Citing this family (70)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7208049B2 (en) * | 2003-10-20 | 2007-04-24 | Air Products And Chemicals, Inc. | Process solutions containing surfactants used as post-chemical mechanical planarization treatment |
US7521405B2 (en) * | 2002-08-12 | 2009-04-21 | Air Products And Chemicals, Inc. | Process solutions containing surfactants |
US6492308B1 (en) * | 1999-11-16 | 2002-12-10 | Esc, Inc. | Post chemical-mechanical planarization (CMP) cleaning composition |
TWI229123B (en) * | 2000-03-03 | 2005-03-11 | Nec Electronics Corp | Anticorrosive treating concentrate |
US6811658B2 (en) * | 2000-06-29 | 2004-11-02 | Ebara Corporation | Apparatus for forming interconnects |
US6310019B1 (en) * | 2000-07-05 | 2001-10-30 | Wako Pure Chemical Industries, Ltd. | Cleaning agent for a semi-conductor substrate |
KR100338777B1 (en) * | 2000-07-22 | 2002-05-31 | 윤종용 | Manufacturing method of semiconductor device for protecting Cu layer from post chemical mechanical polishing-corrosion and chemical mechanical polisher used in the same. |
US6498131B1 (en) * | 2000-08-07 | 2002-12-24 | Ekc Technology, Inc. | Composition for cleaning chemical mechanical planarization apparatus |
US6656894B2 (en) * | 2000-12-07 | 2003-12-02 | Ashland Inc. | Method for cleaning etcher parts |
US6627587B2 (en) * | 2001-04-19 | 2003-09-30 | Esc Inc. | Cleaning compositions |
JP4945857B2 (en) | 2001-06-13 | 2012-06-06 | Jsr株式会社 | Polishing pad cleaning composition and polishing pad cleaning method |
US6653265B2 (en) * | 2001-06-20 | 2003-11-25 | Cornell Research Foundation, Inc. | Removable marking system |
US20030119692A1 (en) * | 2001-12-07 | 2003-06-26 | So Joseph K. | Copper polishing cleaning solution |
US6828226B1 (en) | 2002-01-09 | 2004-12-07 | Taiwan Semiconductor Manufacturing Company, Limited | Removal of SiON residue after CMP |
US7198705B2 (en) * | 2002-12-19 | 2007-04-03 | Texas Instruments Incorporated | Plating-rinse-plating process for fabricating copper interconnects |
US20040175942A1 (en) * | 2003-01-03 | 2004-09-09 | Chang Song Y. | Composition and method used for chemical mechanical planarization of metals |
TWI264620B (en) * | 2003-03-07 | 2006-10-21 | Asml Netherlands Bv | Lithographic apparatus and device manufacturing method |
US6930017B2 (en) * | 2003-08-21 | 2005-08-16 | Micron Technology, Inc. | Wafer Cleaning method and resulting wafer |
US6936534B2 (en) * | 2003-09-17 | 2005-08-30 | Micron Technology, Inc. | Method for the post-etch cleaning of multi-level damascene structures having underlying copper metallization |
KR100795364B1 (en) * | 2004-02-10 | 2008-01-17 | 삼성전자주식회사 | Composition for cleaning a semiconductor substrate, method of cleaning and method for manufacturing a conductive structure using the same |
US7435712B2 (en) * | 2004-02-12 | 2008-10-14 | Air Liquide America, L.P. | Alkaline chemistry for post-CMP cleaning |
US7498295B2 (en) | 2004-02-12 | 2009-03-03 | Air Liquide Electronics U.S. Lp | Alkaline chemistry for post-CMP cleaning comprising tetra alkyl ammonium hydroxide |
US7087564B2 (en) * | 2004-03-05 | 2006-08-08 | Air Liquide America, L.P. | Acidic chemistry for post-CMP cleaning |
US20050205835A1 (en) * | 2004-03-19 | 2005-09-22 | Tamboli Dnyanesh C | Alkaline post-chemical mechanical planarization cleaning compositions |
KR20050110470A (en) * | 2004-05-19 | 2005-11-23 | 테크노세미켐 주식회사 | Composition for cleaning a semiconductor substrate, method for cleaning a semiconductor substrate and method for manufacturing a semiconductor device using the same |
KR20060075315A (en) * | 2004-12-28 | 2006-07-04 | 동부일렉트로닉스 주식회사 | A cleaning method for removing cu compound byproducts for manufacturing a semiconductor device |
US20060148666A1 (en) * | 2004-12-30 | 2006-07-06 | Advanced Technology Materials Inc. | Aqueous cleaner with low metal etch rate |
JP5600376B2 (en) * | 2005-01-27 | 2014-10-01 | 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 | Composition for the treatment of semiconductor substrates |
US7923423B2 (en) * | 2005-01-27 | 2011-04-12 | Advanced Technology Materials, Inc. | Compositions for processing of semiconductor substrates |
US7365045B2 (en) * | 2005-03-30 | 2008-04-29 | Advanced Tehnology Materials, Inc. | Aqueous cleaner with low metal etch rate comprising alkanolamine and tetraalkylammonium hydroxide |
EP2687589A3 (en) * | 2005-05-26 | 2014-05-07 | Advanced Technology Materials, Inc. | Copper passivating post-chemical mechanical polishing cleaning composition and method of use |
JP2008543060A (en) * | 2005-05-26 | 2008-11-27 | 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 | Copper-inactivated chemical mechanical post-polishing cleaning composition and method of use |
EP1891482B1 (en) * | 2005-06-07 | 2014-04-30 | Advanced Technology Materials, Inc. | Metal and dielectric compatible sacrificial anti-reflective coating cleaning and removal composition |
JP2008547202A (en) * | 2005-06-13 | 2008-12-25 | 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 | Compositions and methods for selective removal of metals or metal alloys after formation of metal silicides |
TW200734448A (en) * | 2006-02-03 | 2007-09-16 | Advanced Tech Materials | Low pH post-CMP residue removal composition and method of use |
US7732393B2 (en) * | 2006-03-20 | 2010-06-08 | Cabot Microelectronics Corporation | Oxidation-stabilized CMP compositions and methods |
US20070225186A1 (en) * | 2006-03-27 | 2007-09-27 | Matthew Fisher | Alkaline solutions for post CMP cleaning processes |
US20070232511A1 (en) * | 2006-03-28 | 2007-10-04 | Matthew Fisher | Cleaning solutions including preservative compounds for post CMP cleaning processes |
US8685909B2 (en) | 2006-09-21 | 2014-04-01 | Advanced Technology Materials, Inc. | Antioxidants for post-CMP cleaning formulations |
US20080076688A1 (en) * | 2006-09-21 | 2008-03-27 | Barnes Jeffrey A | Copper passivating post-chemical mechanical polishing cleaning composition and method of use |
EP2082024A4 (en) * | 2006-09-25 | 2010-11-17 | Advanced Tech Materials | Compositions and methods for the removal of photoresist for a wafer rework application |
US20100112728A1 (en) * | 2007-03-31 | 2010-05-06 | Advanced Technology Materials, Inc. | Methods for stripping material for wafer reclamation |
US20090120457A1 (en) * | 2007-11-09 | 2009-05-14 | Surface Chemistry Discoveries, Inc. | Compositions and method for removing coatings and preparation of surfaces for use in metal finishing, and manufacturing of electronic and microelectronic devices |
JP5379441B2 (en) | 2008-10-09 | 2013-12-25 | 関東化学株式会社 | Alkaline aqueous solution composition for substrate processing |
US9074170B2 (en) | 2008-10-21 | 2015-07-07 | Advanced Technology Materials, Inc. | Copper cleaning and protection formulations |
KR101751553B1 (en) | 2009-06-30 | 2017-06-27 | 바스프 에스이 | Aqueous alkaline cleaning compositions and methods of their use |
CN102044474B (en) * | 2009-10-13 | 2015-04-29 | 中芯国际集成电路制造(上海)有限公司 | Surface treatment method of copper metal layer subjected to chemically mechanical polishing |
TWI447224B (en) * | 2009-12-25 | 2014-08-01 | Uwiz Technology Co Ltd | Cleaning composition |
TWI583786B (en) | 2010-01-29 | 2017-05-21 | 恩特葛瑞斯股份有限公司 | Cleaning agent for semiconductor provided with metal wiring |
WO2012011020A2 (en) | 2010-07-19 | 2012-01-26 | Basf Se | Aqueous alkaline cleaning compositions and methods of their use |
KR101827031B1 (en) | 2010-10-06 | 2018-02-07 | 엔테그리스, 아이엔씨. | Composition and process for selectively etching metal nitrides |
KR102064487B1 (en) | 2011-01-13 | 2020-01-10 | 엔테그리스, 아이엔씨. | Formulations for the removal of particles generated by cerium-containing solutions |
CN102420173B (en) * | 2011-06-07 | 2015-04-08 | 上海华力微电子有限公司 | Surface treatment method for improving copper interconnection reliability |
JP5933950B2 (en) | 2011-09-30 | 2016-06-15 | 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 | Etching solution for copper or copper alloy |
SG11201404930SA (en) | 2012-02-15 | 2014-09-26 | Advanced Tech Materials | Post-cmp removal using compositions and method of use |
EP2850495A4 (en) | 2012-05-18 | 2016-01-20 | Entegris Inc | Composition and process for stripping photoresist from a surface including titanium nitride |
US9765288B2 (en) | 2012-12-05 | 2017-09-19 | Entegris, Inc. | Compositions for cleaning III-V semiconductor materials and methods of using same |
CN105102584B (en) | 2013-03-04 | 2018-09-21 | 恩特格里斯公司 | Composition and method for selective etch titanium nitride |
TWI651396B (en) | 2013-06-06 | 2019-02-21 | 美商恩特葛瑞斯股份有限公司 | Compositions and methods for selectively etching titanium nitride |
WO2015017659A1 (en) | 2013-07-31 | 2015-02-05 | Advanced Technology Materials, Inc. | AQUEOUS FORMULATIONS FOR REMOVING METAL HARD MASK AND POST-ETCH RESIDUE WITH Cu/W COMPATIBILITY |
SG10201801575YA (en) | 2013-08-30 | 2018-03-28 | Entegris Inc | Compositions and methods for selectively etching titanium nitride |
KR101964901B1 (en) | 2013-12-06 | 2019-04-02 | 후지필름 일렉트로닉 머티리얼스 유.에스.에이., 아이엔씨. | Cleaning formulation for removing residues on surfaces |
US10340150B2 (en) | 2013-12-16 | 2019-07-02 | Entegris, Inc. | Ni:NiGe:Ge selective etch formulations and method of using same |
JP6776125B2 (en) | 2013-12-20 | 2020-10-28 | インテグリス・インコーポレーテッド | Use of non-oxidizing strong acids for removal of ion-implanted resists |
WO2015103146A1 (en) | 2013-12-31 | 2015-07-09 | Advanced Technology Materials, Inc. | Formulations to selectively etch silicon and germanium |
WO2015116818A1 (en) * | 2014-01-29 | 2015-08-06 | Advanced Technology Materials, Inc. | Post chemical mechanical polishing formulations and method of use |
WO2015116679A1 (en) * | 2014-01-29 | 2015-08-06 | Advanced Technology Materials, Inc. | Post chemical mechanical polishing formulations and method of use |
US11127587B2 (en) | 2014-02-05 | 2021-09-21 | Entegris, Inc. | Non-amine post-CMP compositions and method of use |
SG11202008828VA (en) | 2018-03-28 | 2020-10-29 | Fujifilm Electronic Materials Usa Inc | Cleaning compositions |
WO2020045414A1 (en) | 2018-08-30 | 2020-03-05 | 三菱ケミカル株式会社 | Cleaning liquid, cleaning method and method for producing semiconductor wafer |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0678571A2 (en) * | 1994-04-20 | 1995-10-25 | MALLINCKRODT BAKER, Inc. | pH Adjusted nonionic surfactant containing alkaline cleaner composition for cleaning microelectronics substrates |
EP0812011A2 (en) * | 1996-06-05 | 1997-12-10 | Wako Pure Chemical Industries, Ltd | Cleaning agent |
WO1998022568A1 (en) * | 1996-11-22 | 1998-05-28 | Advanced Chemical Systems International, Inc. | Stripping formulation including catechol, hydroxylamine, non-alkanolamine, water for post plasma ashed wafer cleaning |
US5981454A (en) * | 1993-06-21 | 1999-11-09 | Ekc Technology, Inc. | Post clean treatment composition comprising an organic acid and hydroxylamine |
Family Cites Families (43)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4168989A (en) | 1975-06-10 | 1979-09-25 | Westinghouse Electric Corp. | Stripping composition for thermoset resins and method of repairing electrical apparatus |
US4294729A (en) | 1979-12-17 | 1981-10-13 | International Business Machines Corporation | Composition containing alcohol and use thereof for epoxy removal |
US4487708A (en) | 1980-07-14 | 1984-12-11 | Betz Laboratories, Inc. | Hydroquinone oxygen scavenger for use in aqueous mediums |
US4395348A (en) | 1981-11-23 | 1983-07-26 | Ekc Technology, Inc. | Photoresist stripping composition and method |
JPS59219743A (en) | 1983-05-28 | 1984-12-11 | Tokyo Ohka Kogyo Co Ltd | Positive type resist developing solution |
US4617251A (en) | 1985-04-11 | 1986-10-14 | Olin Hunt Specialty Products, Inc. | Stripping composition and method of using the same |
DE3523088A1 (en) | 1985-06-28 | 1987-01-08 | Hoechst Ag | METHOD FOR AVOIDING CORROSION OF METAL MATERIALS |
JPH0626708B2 (en) | 1985-09-10 | 1994-04-13 | 関西ペイント株式会社 | Composite coating formation method |
DE3537441A1 (en) | 1985-10-22 | 1987-04-23 | Hoechst Ag | SOLVENT FOR REMOVING PHOTORESISTS |
US4744834A (en) | 1986-04-30 | 1988-05-17 | Noor Haq | Photoresist stripper comprising a pyrrolidinone, a diethylene glycol ether, a polyglycol and a quaternary ammonium hydroxide |
US4770713A (en) | 1986-12-10 | 1988-09-13 | Advanced Chemical Technologies, Inc. | Stripping compositions containing an alkylamide and an alkanolamine and use thereof |
US5185235A (en) | 1987-09-09 | 1993-02-09 | Tokyo Ohka Kogyo Co., Ltd. | Remover solution for photoresist |
US5190723A (en) | 1988-02-25 | 1993-03-02 | Ciba-Geigy Corporation | Process for inhibiting corrosion |
US5091103A (en) | 1990-05-01 | 1992-02-25 | Alicia Dean | Photoresist stripper |
US5279771A (en) | 1990-11-05 | 1994-01-18 | Ekc Technology, Inc. | Stripping compositions comprising hydroxylamine and alkanolamine |
JP3160344B2 (en) | 1991-01-25 | 2001-04-25 | アシュランド インコーポレーテッド | Organic stripping composition |
US5988186A (en) | 1991-01-25 | 1999-11-23 | Ashland, Inc. | Aqueous stripping and cleaning compositions |
US5753601A (en) | 1991-01-25 | 1998-05-19 | Ashland Inc | Organic stripping composition |
US5496491A (en) | 1991-01-25 | 1996-03-05 | Ashland Oil Company | Organic stripping composition |
US5556482A (en) | 1991-01-25 | 1996-09-17 | Ashland, Inc. | Method of stripping photoresist with composition containing inhibitor |
US5308745A (en) | 1992-11-06 | 1994-05-03 | J. T. Baker Inc. | Alkaline-containing photoresist stripping compositions producing reduced metal corrosion with cross-linked or hardened resist resins |
US5391258A (en) | 1993-05-26 | 1995-02-21 | Rodel, Inc. | Compositions and methods for polishing |
US5407788A (en) | 1993-06-24 | 1995-04-18 | At&T Corp. | Photoresist stripping method |
US5419877A (en) | 1993-09-17 | 1995-05-30 | General Atomics | Acoustic barrier separator |
US6326130B1 (en) | 1993-10-07 | 2001-12-04 | Mallinckrodt Baker, Inc. | Photoresist strippers containing reducing agents to reduce metal corrosion |
US5419779A (en) | 1993-12-02 | 1995-05-30 | Ashland Inc. | Stripping with aqueous composition containing hydroxylamine and an alkanolamine |
US5567574A (en) * | 1995-01-10 | 1996-10-22 | Mitsubishi Gas Chemical Company, Inc. | Removing agent composition for photoresist and method of removing |
US5597420A (en) | 1995-01-17 | 1997-01-28 | Ashland Inc. | Stripping composition having monoethanolamine |
US5563119A (en) * | 1995-01-26 | 1996-10-08 | Ashland Inc. | Stripping compositions containing alkanolamine compounds |
US5783495A (en) | 1995-11-13 | 1998-07-21 | Micron Technology, Inc. | Method of wafer cleaning, and system and cleaning solution regarding same |
KR100360394B1 (en) | 1995-12-20 | 2003-01-24 | 삼성전자 주식회사 | Method for cleaning semiconductor substrate and cleaning solution used for the same |
US5704987A (en) | 1996-01-19 | 1998-01-06 | International Business Machines Corporation | Process for removing residue from a semiconductor wafer after chemical-mechanical polishing |
US5648324A (en) | 1996-01-23 | 1997-07-15 | Ocg Microelectronic Materials, Inc. | Photoresist stripping composition |
US5665688A (en) | 1996-01-23 | 1997-09-09 | Olin Microelectronics Chemicals, Inc. | Photoresist stripping composition |
KR100207469B1 (en) | 1996-03-07 | 1999-07-15 | 윤종용 | Cleaning solution for semiconductor substrate and cleaning method thereby |
US5932021A (en) | 1996-06-26 | 1999-08-03 | Cala; Francis R. | Aqueous cleaning composition for removing flux and method of use |
US5855811A (en) | 1996-10-03 | 1999-01-05 | Micron Technology, Inc. | Cleaning composition containing tetraalkylammonium salt and use thereof in semiconductor fabrication |
US5709756A (en) | 1996-11-05 | 1998-01-20 | Ashland Inc. | Basic stripping and cleaning composition |
US5698503A (en) | 1996-11-08 | 1997-12-16 | Ashland Inc. | Stripping and cleaning composition |
US5756398A (en) | 1997-03-17 | 1998-05-26 | Rodel, Inc. | Composition and method for polishing a composite comprising titanium |
US5922136A (en) | 1997-03-28 | 1999-07-13 | Taiwan Semiconductor Manufacturing Company, Ltd. | Post-CMP cleaner apparatus and method |
US5935871A (en) | 1997-08-22 | 1999-08-10 | Motorola, Inc. | Process for forming a semiconductor device |
US5997658A (en) * | 1998-01-09 | 1999-12-07 | Ashland Inc. | Aqueous stripping and cleaning compositions |
-
1999
- 1999-11-16 US US09/440,917 patent/US6194366B1/en not_active Expired - Lifetime
-
2000
- 2000-11-16 WO PCT/US2000/042197 patent/WO2001040425A2/en active Application Filing
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5981454A (en) * | 1993-06-21 | 1999-11-09 | Ekc Technology, Inc. | Post clean treatment composition comprising an organic acid and hydroxylamine |
EP0678571A2 (en) * | 1994-04-20 | 1995-10-25 | MALLINCKRODT BAKER, Inc. | pH Adjusted nonionic surfactant containing alkaline cleaner composition for cleaning microelectronics substrates |
EP0812011A2 (en) * | 1996-06-05 | 1997-12-10 | Wako Pure Chemical Industries, Ltd | Cleaning agent |
WO1998022568A1 (en) * | 1996-11-22 | 1998-05-28 | Advanced Chemical Systems International, Inc. | Stripping formulation including catechol, hydroxylamine, non-alkanolamine, water for post plasma ashed wafer cleaning |
Cited By (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6723691B2 (en) | 1999-11-16 | 2004-04-20 | Advanced Technology Materials, Inc. | Post chemical-mechanical planarization (CMP) cleaning composition |
WO2002065538A3 (en) * | 2001-02-12 | 2003-02-13 | Esc Inc | Post chemical-mechanical planarization (cmp) cleaning composition |
WO2002065538A2 (en) * | 2001-02-12 | 2002-08-22 | Esc, Inc. | Post chemical-mechanical planarization (cmp) cleaning composition |
EP1845555A1 (en) * | 2001-02-12 | 2007-10-17 | ESC Inc. | Post chemical-mechanical planarization (CMP) cleaning composition |
CN100410359C (en) * | 2001-07-09 | 2008-08-13 | 马林克罗特贝克公司 | Ammonia-free alkaline microelectronic cleaning compositions with improved substrate compatibility |
WO2003006598A1 (en) * | 2001-07-09 | 2003-01-23 | Mallinckrodt Baker Inc. | Ammonia-free alkaline microelectronic cleaning compositions with improved substrate compatibility |
US7718591B2 (en) | 2001-07-09 | 2010-05-18 | Mallinckrodt Baker, Inc. | Microelectronic cleaning compositions containing ammonia-free fluoride salts for selective photoresist stripping and plasma ash residue cleaning |
US7247208B2 (en) | 2001-07-09 | 2007-07-24 | Mallinckrodt Baker, Inc. | Microelectronic cleaning compositions containing ammonia-free fluoride salts |
US7393819B2 (en) | 2002-07-08 | 2008-07-01 | Mallinckrodt Baker, Inc. | Ammonia-free alkaline microelectronic cleaning compositions with improved substrate compatibility |
WO2005066325A2 (en) * | 2003-12-31 | 2005-07-21 | Ekc Technology, Inc. | Cleaner compositions containing free radical quenchers |
WO2005066325A3 (en) * | 2003-12-31 | 2006-03-30 | Ekc Technology Inc | Cleaner compositions containing free radical quenchers |
US8012973B2 (en) | 2005-10-14 | 2011-09-06 | Proyecto De Biomedicina Cima S.L. | Compounds for the treatment of auricular fibrillation |
WO2016011331A1 (en) * | 2014-07-18 | 2016-01-21 | Cabot Microelectronics Corporation | Cleaning composition following cmp and methods related thereto |
CN106661518A (en) * | 2014-07-18 | 2017-05-10 | 嘉柏微电子材料股份公司 | Cleaning composition following CMP and methods related thereto |
EP3169765A4 (en) * | 2014-07-18 | 2018-03-28 | Cabot Microelectronics Corporation | Cleaning composition following cmp and methods related thereto |
US10100272B2 (en) | 2014-07-18 | 2018-10-16 | Cabot Microelectronics Corporation | Cleaning composition following CMP and methods related thereto |
CN106661518B (en) * | 2014-07-18 | 2020-01-14 | 嘉柏微电子材料股份公司 | Cleaning compositions for post-CMP use and methods relating thereto |
CN107208005A (en) * | 2015-01-13 | 2017-09-26 | 嘉柏微电子材料股份公司 | Cleasing compositions and method for the clean semiconductor chip after chemically mechanical polishing |
Also Published As
Publication number | Publication date |
---|---|
US6194366B1 (en) | 2001-02-27 |
WO2001040425A3 (en) | 2002-01-03 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US6194366B1 (en) | Post chemical-mechanical planarization (CMP) cleaning composition | |
JP4942275B2 (en) | Cleaning composition after chemical mechanical planarization (CMP) | |
EP1360712B1 (en) | Post chemical-mechanical planarization (cmp) cleaning composition | |
US7365045B2 (en) | Aqueous cleaner with low metal etch rate comprising alkanolamine and tetraalkylammonium hydroxide | |
EP1888735B1 (en) | Copper passivating post-chemical mechanical polishing cleaning composition and method of use | |
US20060148666A1 (en) | Aqueous cleaner with low metal etch rate | |
KR100913557B1 (en) | Liquid detergent for semiconductor device substrate and method of cleaning | |
KR101166002B1 (en) | Substrate cleaning liquid for semiconductor device and cleaning method | |
KR100867287B1 (en) | Detergent composition | |
JP4550838B2 (en) | Improved alkaline chemical product for post-cleaning of chemical mechanical planarization | |
US20080076688A1 (en) | Copper passivating post-chemical mechanical polishing cleaning composition and method of use | |
KR20100100841A (en) | Method and solution for washing substrate for semiconductor device | |
KR102242969B1 (en) | Semi-conductor substrate cleaning solution composition | |
EP2687589A2 (en) | Copper passivating post-chemical mechanical polishing cleaning composition and method of use | |
JP2015203047A (en) | Substrate cleaning liquid for semiconductor device and method for cleaning substrate for semiconductor device |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A2 Designated state(s): CN JP KR |
|
AL | Designated countries for regional patents |
Kind code of ref document: A2 Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
AK | Designated states |
Kind code of ref document: A3 Designated state(s): CN JP KR |
|
AL | Designated countries for regional patents |
Kind code of ref document: A3 Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR |
|
122 | Ep: pct application non-entry in european phase |