US20080200361A1 - Aqueous cleaner with low metal etch rate - Google Patents
Aqueous cleaner with low metal etch rate Download PDFInfo
- Publication number
- US20080200361A1 US20080200361A1 US12/111,469 US11146908A US2008200361A1 US 20080200361 A1 US20080200361 A1 US 20080200361A1 US 11146908 A US11146908 A US 11146908A US 2008200361 A1 US2008200361 A1 US 2008200361A1
- Authority
- US
- United States
- Prior art keywords
- alkanolamine
- cleaning
- copper
- monoethanolamine
- quaternary ammonium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 229910052751 metal Inorganic materials 0.000 title abstract description 18
- 239000002184 metal Substances 0.000 title abstract description 18
- 238000004140 cleaning Methods 0.000 claims abstract description 92
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims abstract description 51
- 125000001453 quaternary ammonium group Chemical group 0.000 claims abstract description 48
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims abstract description 38
- 239000000908 ammonium hydroxide Substances 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000000203 mixture Substances 0.000 claims description 69
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 43
- 238000000034 method Methods 0.000 claims description 29
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 claims description 18
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 claims description 17
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 16
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 8
- YSAANLSYLSUVHB-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]ethanol Chemical compound CN(C)CCOCCO YSAANLSYLSUVHB-UHFFFAOYSA-N 0.000 claims description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 claims 1
- 238000001914 filtration Methods 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 28
- 238000004377 microelectronic Methods 0.000 abstract description 15
- 150000001412 amines Chemical class 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 78
- 239000010949 copper Substances 0.000 description 70
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 69
- 229910052802 copper Inorganic materials 0.000 description 69
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 47
- 235000011114 ammonium hydroxide Nutrition 0.000 description 43
- 230000007797 corrosion Effects 0.000 description 27
- 238000005260 corrosion Methods 0.000 description 27
- 235000012431 wafers Nutrition 0.000 description 27
- 239000002245 particle Substances 0.000 description 20
- 238000009472 formulation Methods 0.000 description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- 229910052782 aluminium Inorganic materials 0.000 description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 239000004065 semiconductor Substances 0.000 description 11
- 229910052721 tungsten Inorganic materials 0.000 description 11
- 229920002120 photoresistant polymer Polymers 0.000 description 10
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 10
- 239000010937 tungsten Substances 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000006117 anti-reflective coating Substances 0.000 description 7
- 239000003112 inhibitor Substances 0.000 description 7
- 238000005498 polishing Methods 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 238000011282 treatment Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 238000011256 aggressive treatment Methods 0.000 description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 238000011109 contamination Methods 0.000 description 4
- 229940074391 gallic acid Drugs 0.000 description 4
- 235000004515 gallic acid Nutrition 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 229940079877 pyrogallol Drugs 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000011668 ascorbic acid Substances 0.000 description 2
- 235000010323 ascorbic acid Nutrition 0.000 description 2
- 229960005070 ascorbic acid Drugs 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- PMFOYSPPKBXFCT-UHFFFAOYSA-N 2-[bis(2-hydroxyethyl)amino]ethanol;2-(methylamino)ethanol Chemical compound CNCCO.OCCN(CCO)CCO PMFOYSPPKBXFCT-UHFFFAOYSA-N 0.000 description 1
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-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
- 150000000996 L-ascorbic acids Chemical class 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- FZUWSDSLCFAWAG-UHFFFAOYSA-N [Cu].[K].[Cu] Chemical compound [Cu].[K].[Cu] FZUWSDSLCFAWAG-UHFFFAOYSA-N 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 230000007547 defect Effects 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
- ZOSVFAIIFHTUEG-UHFFFAOYSA-L dipotassium;dihydroxide Chemical compound [OH-].[OH-].[K+].[K+] ZOSVFAIIFHTUEG-UHFFFAOYSA-L 0.000 description 1
- 238000001035 drying Methods 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
- 230000007717 exclusion Effects 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000673 graphite furnace atomic absorption spectrometry Methods 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 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
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 230000008698 shear stress Effects 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000004334 sorbic acid Substances 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
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02041—Cleaning
- H01L21/02057—Cleaning during device manufacture
- H01L21/02068—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers
- H01L21/02074—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers the processing being a planarization of conductive layers
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/06—Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—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
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/32—Alkaline compositions
- C23F1/34—Alkaline compositions for etching copper or alloys thereof
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
- C23G1/16—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions using inhibitors
- C23G1/18—Organic inhibitors
-
- 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
-
- C11D2111/22—
Definitions
- the present invention relates to post etch and post chemical-mechanical polishing (post-CMP) cleaning operations, and more specifically to post etch and post-CMP cleaning solutions for metal-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 and post etch processes are now well established enabling technology used by most advanced semiconductor operations for manufacturing of semi-conductor 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.
- a majority of CMP applications have been directed to aluminum, tungsten, tantalum, and oxide-containing surfaces.
- 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.
- CMP processes 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.
- Patentees disclose a cleaning composition containing tetramethyl-ammonium hydroxide (TMAH), monoethanol amine (MEA), a corrosion inhibitor being one of gallic acid ascorbic acid or mixtures thereof and water.
- TMAH tetramethyl-ammonium hydroxide
- MEA monoethanol amine
- the basic composition can be used in a dilute form for effective Post CMP cleaning.
- 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 70 to 95 wt % monoethanolamine and a corrosion inhibitor at about 5 wt % such as catechol, pyrogallol or gallic acid.
- the pH of the solution is greater than 8.
- the solution may further contain a corrosion inhibitor such as gallic acid, catechol, or pyrogallol.
- Ilardi et al. U.S. Pat. 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.
- Ward U.S. Pat. No. 5,563,119 discloses a post etch aqueous stripping composition consisting of an alkanolamine, tetraalkyammonium hydroxide, and a corrosion inhibitor for cleaning organic residue from aluminized inorganic substrates.
- post-CMP cleaning compositions for copper-containing surfaces to not only clean residuals particles and contaminants from surfaces of devices but to further 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.
- the present invention is a cleaning solution for cleaning metal-containing microelectronic substrates consisting of 0.09 to 22% by weight alkanolamine, 0.02 to 13.5% by weight quaternary ammonium hydroxide, balance deionized water.
- the pH of the solution should be greater than 10.
- the present invention is a post-CMP cleaning solution for cleaning microelectronic substrates consisting of 0.09 to 22 wt % of an alkanolamine selected from the group consisting of monoethanolamine, 1, amino-2-propanol, 2-(methylamino) ethanol, triethanolamine and mixtures thereof, a quaternary ammonium hydroxide selected from the group consisting of tetramethylammonium hydroxide, tetrabutyl ammonium hydroxide and mixtures thereof in an amount in the range from about 0.02 wt % to about 13.5 wt %, balance deionized water.
- an alkanolamine selected from the group consisting of monoethanolamine, 1, amino-2-propanol, 2-(methylamino) ethanol, triethanolamine and mixtures thereof
- a quaternary ammonium hydroxide selected from the group consisting of tetramethylammonium hydroxide, tetrabutyl ammonium hydroxide and mixtures thereof in
- the present invention is a cleaning composition containing 9.0 wt % to 22.0 wt % alkanolamine, 0.45 wt % to 12.2 wt % quaternary ammonium hydroxide, balance deionized water.
- the present invention is a cleaning composition consisting essentially of 0.30 to 0.70 wt % alkanolamine 0.02 to 0.7 wt % quaternary ammonium hydroxide, balance deionized water.
- the present invention is a cleaning composition consisting essentially of 0.30 to 9.0 wt % alkanolamine, 0.06 to 13.5 wt % potassium hydroxide, balance deionized water.
- FIG. 1 is a scanning electron microscope (SEM) photomicrograph of a wafer prepared with an aggressive cleaning composition according to the invention.
- FIG. 2 is a scanning electron microscope (SEM) photomicrograph of a wafer cleaned in a less aggressive composition according to the present invention.
- FIG. 3 is a SEM photomicrograph of the device shown in FIG. 1 treated to strip photoresist with an aggressive composition according to the invention.
- FIG. 4 is a SEM photomicrograph of a device shown in FIG. 1 treated to strip photoresist with a less aggressive composition according to the invention.
- FIG. 5 is a pair of SEM photomicrographs of a patterned wafer before treatment with a composition according to the invention.
- FIG. 6 is a SEM photomicrograph of post etch short-looped patterned wafer segments after treatment with a composition according to the present invention.
- FIG. 7 is a SEM photomicrograph of another portion of the device of FIG. 6 treated post etch with a composition according to the invention.
- 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 a copper alloy. It is understood that the microelectronic surface may also be composed of semiconductor materials, such as AL, W, 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 quaternary ammonium hydroxide, an amine, and the balance deionized water.
- the pH of a cleaning solution of the invention is greater than 10.
- the constituents of the cleaning solutions of the invention may be mixed together in any order.
- the order of addition is exemplified with respect to the embodiment containing TMAH, MEA, and deionized water.
- 100% of the water in the final solution is added to all of the MEA.
- 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.
- An important feature of the cleaning solutions of the invention is that only two non-aqueous constituents (the constituents other than water) are present in the solution.
- compositions of invention consist of a quaternary ammonium hydroxide in an amount in the range from about 0.02 to about 13.5 wt %, an alkanolamine in an amount in the range from about 0.3 to about 22.0 wt %, and the balance water (preferably deionized water).
- compositions of the invention preferably use one or a mixture of tetramethylammonium hydroxide (TMAH) or tetrabutylammonium hydroxide (TBAH) as the quaternary ammonium hydroxide.
- TMAH tetramethylammonium hydroxide
- TBAH tetrabutylammonium hydroxide
- the alkanolamine is preferably monoethanolamine (MEA) 1-amino-2-propanol (1A2P), 2-(methylamino) ethanol triethanolamine (TEA) and mixtures thereof.
- the cleaning solutions 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 may adversely alter the chemistry of the cleaning system over time in a process open to ambient conditions.
- the cleaning solutions of the invention have a pH greater than 10. More preferably, the pH of cleaning solutions 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 to avoid redeposition of the remaining particulates during the cleaning operation.
- 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 200 mm wafer, with a 5 mm edge exclusion.
- the cleaning solutions of the invention limit copper corrosion to smoothing of the surface and do not damage processing equipment.
- the cleaning solutions 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 solutions 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. Vias are formed by 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.
- Cleaning solutions were evaluated for the ability to remove particles from wafers patterned with copper into a low-K organosilicon dielectric. These received a final copper chemical mechanical polish (CMP) using a Hitachi low pH barrier slurry followed by drying without post-CMP cleaning.
- CMP copper chemical mechanical polish
- Aqueous solutions of alkanolamines with and without added quaternary ammonium hydroxides similar to Examples 1 and 2 were prepared and diluted 30:1 with water. These diluted solutions were used to clean pieces of the dirty wafers described above.
- a single wafer spray tool operating at 150 rpm at room temperature for 60 seconds was used. Particle counts of 20 ⁇ 20 micron squares were obtained from scanning electron microscope images using the Object Count routine of Sigma Scan Pro software.
- quaternary ammonium hydroxide-containing alkanolamine cleaning solutions were further demonstrated by using such a solution to strip a typical photoresist and anti-reflective coating (ARC) on a copper substrate.
- the test wafer was prepared by spin coating 0.2 micron of Brewer Science bottom-ARC #XL-20 onto a copper layer that had been deposited on a silicon wafer.
- the ARC was cured by baking at 190° C. followed by further spin coating with four microns of Shipley SPR-220 photoresist.
- the photoresist was then cured by baking at 140° C. followed by a one minute deep UV cure at the same temperature. Pieces of this wafer were stripped using a mixture of 92% monoethanolamine, 2% tetramethylammonium hydroxide, and 6% water under the following process conditions.
- FIG. 1 illustrates the absence of any damage to the copper surface using most aggressive treatment. Further evidence of copper compatibility was obtained by measuring the copper etch rate of the formulation prepared above using the sheet resistance method described in Example 2. A copper etch rate of 4.3 Angstroms/minute at 70° C. was obtained which is similar to the improved etch rates reported for the formulations described in Example 2.
- FIG. 2 illustrates the complete removal of ARC and photoresist using the least aggressive treatment.
- FIG. 3 illustrates the absence of any damage to the copper surface using the most aggressive treatment. Further evidence of copper compatibility was obtained by measuring the copper etch rate of the formulation prepared above using the sheet resistance method described in Example 2. A favorably low copper etch rate of 2.4 Angstroms/minute at 70° C. was obtained.
- FIG. 4 illustrates the complete removal of ARC and photoresist using a much less aggressive treatment.
- potassium hydroxide is an effective alternate to the quaternary ammonium hydroxide for use in an effective cleaning solution.
- Examples 7 and 8 set out below summarize data for compositions using an amine, (e.g. MEA), potassium hydroxide (KOH) and deionized water.
- Additional short-loop patterned test wafers containing organosilicon glass (OSG) patterns on ECD copper and blanket ECD copper wafers were used in testing of the composition of the invention.
- organosilicon glass (OSG) patterns on ECD copper and blanket ECD copper wafers were used in testing of the composition of the invention.
- FIG. 5 is a pair of photomicrographs of the device prior to being exposed to the cleaning composition.
- FIG. 6 and FIG. 7 are photomicrographs of the device of FIG. 5 after exposure to the cleaning composition for 10 minutes at 50° C.
- Aqueous solutions of an alkanolamine (monoethanolamine) with and without an added quaternary ammonium hydroxide ([carboxymethyl]trimethylammonium hydroxide inner salt) were prepared:
- Coupons of 99.8% aluminum were cleaned in water, isopropanol, dried and weighed. Coupons were heated in solutions C and D for 3 hours at 65° C., the coupons were removed, rinsed with water, isopropanol, dried and reweighed. Weight losses were converted to the following corrosion rates:
- Coupons of 99.9+% tungsten were cleaned in water, then acetone, dried and weighed. Coupons were heated in solutions E and F for 5 hours at 85° C., the coupons were removed, rinsed with water, then acetone, dried and reweighed. Weight losses were converted to the following corrosion rates:
Abstract
A cleaning solution is provided for cleaning metal-containing microelectronic substrates, particularly for post etch, via formation and post CMP cleaning. The cleaning solution consists of a quaternary ammonium hydroxide, an organic amine, and water. A preferred cleaning solution consists of tetramethylammonium hydroxide, monoethanolamine, and water. The pH of cleaning solution is greater than 10.
Description
- This is a continuation of the U.S. patent application Ser. No. 11/094,113 for “Aqueous Cleaner with Low Metal Etch Rate” filed on Mar. 30, 2005 in the name of Elizabeth Walker et al., which is hereby incorporated by reference in its entirety.
- The present invention relates to post etch and post chemical-mechanical polishing (post-CMP) cleaning operations, and more specifically to post etch and post-CMP cleaning solutions for metal-containing microelectronic substrates.
- The present day fabrication of semiconductor devices is a complex, multi-step process. The CMP process and post etch processes are now well established enabling technology used by most advanced semiconductor operations for manufacturing of semi-conductor 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. A majority of CMP applications have been directed to aluminum, tungsten, tantalum, and oxide-containing surfaces.
- 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. There are several post-CMP processes 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.
- Effective post-CMP cleaning solutions are disclosed and claimed in U.S. Pat. No. 6,194,366 B1 now owned by the Assignee of the present application. Patentees disclose a cleaning composition containing tetramethyl-ammonium hydroxide (TMAH), monoethanol amine (MEA), a corrosion inhibitor being one of gallic acid ascorbic acid or mixtures thereof and water. The basic composition can be used in a dilute form for effective Post CMP cleaning.
- Nam, U.S. Pat. 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. Pat. No. 5,597,420, discloses a post etch 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 70 to 95 wt % monoethanolamine and a corrosion inhibitor at about 5 wt % such as catechol, pyrogallol or gallic acid.
- Ward, U.S. Pat. No. 5,709,756, discloses a post etch cleaning composition containing about 25 to 48 wt % hydroxylamine, 1 to 20 wt % ammonium fluoride, and water. The pH of the solution is greater than 8. The solution may further contain a corrosion inhibitor such as gallic acid, catechol, or pyrogallol.
- Ilardi et al., U.S. Pat. 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.
- Schwartzkopf et al., European Patent No. 0647884A1 discloses photoresist strippers containing reducing agents to reduce metal corrosion. This patent teaches the use of ascorbic acid, gallic acid, and pyrogallol among others for the control of metal corrosion in alkali containing components.
- U.S. Pat. No. 5,143,648 to Satoh et al., which is herein incorporated by reference discloses novel ascorbic acid derivatives as antioxidants.
- Ward U.S. Pat. No. 5,563,119 discloses a post etch aqueous stripping composition consisting of an alkanolamine, tetraalkyammonium hydroxide, and a corrosion inhibitor for cleaning organic residue from aluminized inorganic substrates.
- From the above noted prior art and general knowledge of workers skilled in the art cleaning compositions known prior to the invention described below required a corrosion inhibitor. Furthermore, in view of the fact that since alkanolamine and a quaternary ammonium hydroxide in combination are each considered corrosive toward most metals, a combination of these two compounds would not be considered by a worker skilled in the art looking for new metal cleaning compositions.
- There is a need to further improve post-CMP cleaning compositions for copper-containing surfaces to not only clean residuals particles and contaminants from surfaces of devices but to further 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.
- In one aspect the present invention is a cleaning solution for cleaning metal-containing microelectronic substrates consisting of 0.09 to 22% by weight alkanolamine, 0.02 to 13.5% by weight quaternary ammonium hydroxide, balance deionized water. The pH of the solution should be greater than 10.
- In another aspect the present invention is a post-CMP cleaning solution for cleaning microelectronic substrates consisting of 0.09 to 22 wt % of an alkanolamine selected from the group consisting of monoethanolamine, 1, amino-2-propanol, 2-(methylamino) ethanol, triethanolamine and mixtures thereof, a quaternary ammonium hydroxide selected from the group consisting of tetramethylammonium hydroxide, tetrabutyl ammonium hydroxide and mixtures thereof in an amount in the range from about 0.02 wt % to about 13.5 wt %, balance deionized water.
- In yet another aspect the present invention is a cleaning composition containing 9.0 wt % to 22.0 wt % alkanolamine, 0.45 wt % to 12.2 wt % quaternary ammonium hydroxide, balance deionized water.
- In still another embodiment the present invention is a cleaning composition consisting essentially of 0.30 to 0.70 wt % alkanolamine 0.02 to 0.7 wt % quaternary ammonium hydroxide, balance deionized water.
- In a further embodiment the present invention is a cleaning composition consisting essentially of 0.30 to 9.0 wt % alkanolamine, 0.06 to 13.5 wt % potassium hydroxide, balance deionized water.
-
FIG. 1 is a scanning electron microscope (SEM) photomicrograph of a wafer prepared with an aggressive cleaning composition according to the invention. -
FIG. 2 is a scanning electron microscope (SEM) photomicrograph of a wafer cleaned in a less aggressive composition according to the present invention. -
FIG. 3 is a SEM photomicrograph of the device shown inFIG. 1 treated to strip photoresist with an aggressive composition according to the invention. -
FIG. 4 is a SEM photomicrograph of a device shown inFIG. 1 treated to strip photoresist with a less aggressive composition according to the invention. -
FIG. 5 is a pair of SEM photomicrographs of a patterned wafer before treatment with a composition according to the invention. -
FIG. 6 is a SEM photomicrograph of post etch short-looped patterned wafer segments after treatment with a composition according to the present invention. -
FIG. 7 is a SEM photomicrograph of another portion of the device ofFIG. 6 treated post etch with a composition according to the invention. - Cleaning metal-containing substrates following CMP processing are 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 a copper alloy. It is understood that the microelectronic surface may also be composed of semiconductor materials, such as AL, W, 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 quaternary ammonium hydroxide, an amine, and the balance deionized water.
- The pH of a cleaning solution of the invention is greater than 10.
- The constituents of the cleaning solutions of the invention may be mixed together in any order. The order of addition is exemplified with respect to the embodiment containing TMAH, MEA, and deionized water. In a preferred method of preparation, 100% of the water in the final solution is added to all of the MEA. 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 of a cleaning solution of the invention are commercially available.
- An important feature of the cleaning solutions of the invention is that only two non-aqueous constituents (the constituents other than water) are present in the solution.
- The compositions of invention consist of a quaternary ammonium hydroxide in an amount in the range from about 0.02 to about 13.5 wt %, an alkanolamine in an amount in the range from about 0.3 to about 22.0 wt %, and the balance water (preferably deionized water).
- The compositions of the invention preferably use one or a mixture of tetramethylammonium hydroxide (TMAH) or tetrabutylammonium hydroxide (TBAH) as the quaternary ammonium hydroxide. The alkanolamine is preferably monoethanolamine (MEA) 1-amino-2-propanol (1A2P), 2-(methylamino) ethanol triethanolamine (TEA) and mixtures thereof.
- The cleaning solutions 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 may adversely alter the chemistry of the cleaning system over time in a process open to ambient conditions.
- The cleaning solutions of the invention, as noted, have a pH greater than 10. More preferably, the pH of cleaning solutions 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 to avoid redeposition of the remaining particulates during the cleaning operation.
- The cleaning solutions of the invention meet 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 200 mm wafer, with a 5 mm edge exclusion.
- The cleaning solutions of the invention limit copper corrosion to smoothing of the surface and do not damage processing equipment.
- The cleaning solutions 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 solutions 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. Vias are formed by 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.
- A series of tests were conducted to determine whether compositions according to the invention while being effective cleaning compositions could cause un-wanted and/or excessive corrosion of copper used in fabricating micro-electronic devices.
- The following examples summarize the data. In the data presented in Tables 1, 2 and 3 the left hand column lists the amine plus deionized water composition and the resulting copper concentration while the right hand column shows the data for the amine and water to which is added quaternary ammonium hydroxide.
- Cleaning solutions were evaluated for the tendency to corrode copper. One hundred milliliter aqueous solutions of alkanolamines with and without added quaternary ammonium hydroxides were prepared. Identical (4×0.02) inch copper wire samples were placed into these solutions for 10 minutes at 22° C., the wire was removed, and the solutions analyzed for copper (in parts per billion) using graphite furnace atomic absorption spectroscopy. The results, set forth in Table 1, clearly show the ability of quaternary ammonium hydroxides to prevent or moderate the copper corrosion (as measured by copper uptake in the cleaning solutions) that accompanies exposure to alkanolamines. Relative copper corrosion rate=(copper content of formulation with quaternary ammonium hydroxide)÷(copper content of formulation without quaternary ammonium hydroxide).
-
TABLE 1 Effect of Quaternary Ammonium Hydroxides on Alkanolamine Cleaners Comparative Alkanolamine Alkanolamine Formulation Solutions without Containing Quaternary Ammonium Hydroxides Quaternary Ammonium Hydroxide Copper Quaternary Copper Content Ammonium Content Relative Alkanolamine wt. % (ppb) Hydroxide wt. % (ppb) Corrosion Rate Monoethanolamine 9 505 Tetramethyl 0.45 455 0.9 Monoethanolamine 9 Tetramethyl 1.8 380 0.8 Monoethanolamine 9 Tetramethyl 5 290 0.6 Monoethanolamine 9 Tetramethyl 9 80 0.2 1-Amino-2-propanol 11 588 Tetramethyl 1.1 613 1.0 1-Amino-2-propanol 11 Tetramethyl 2.2 409 0.7 1-Amino-2-propanol 11 Tetramethyl 3.7 480 0.8 1-Amino-2-propanol 11 Tetramethyl 6.1 404 0.7 1-Amino-2-propanol 11 Tetramethyl 11.0 287 0.5 2-(Methylamino)ethanol 11 344 Tetrabutyl 0.6 225 0.6 2-(Methylamino)ethanol 11 Tetrabutyl 1.1 212 0.6 2-(Methylamino)ethanol 11 Tetrabutyl 2.2 149 0.4 2-(Methylamino)ethanol 11 Tetrabutyl 3.7 133 0.4 2-(Methylamino)ethanol 11 Tetrabutyl 6.1 110 0.3 2-(Methylamino)ethanol 11 Tetrabutyl 11 28 0.08 Triethanolamine 22 190 Tetramethyl 1.1 46 0.2 Triethanolamine 22 Tetramethyl 2.2 0 0 Triethanolamine 22 Tetramethyl 4.4 0 0 Triethanolamine 22 Tetramethyl 7.3 0 0 Triethanolamine 22 Tetramethyl 12.2 0 0 - Cleaning solutions were evaluated for the tendency to corrode copper. Aqueous solutions of alkanolamines with and without added quaternary ammonium hydroxides were prepared. Identical blanket copper on silicon wafer pieces were submersed in these stirred solutions for 10 minutes at 22° C. Four point probe measurements for sheet resistance were made on these pieces prior to and after treatment. Copper etch rates (in Angstroms per minute) for the solutions were calculated. The results, set forth in Table 2, clearly show the ability of quaternary ammonium hydroxides to prevent or moderate the copper corrosion (as measured by copper etch rate) that accompanies exposure to alkanolamines. Relative copper corrosion rate=(copper etch rate of formulation with quaternary ammonium hydroxide)÷(copper etch rate of formulation without quaternary ammonium hydroxide).
-
TABLE 2 Effect of Quaternary Ammonium Hydroxides on Alkanolamine Cleaners Comparative Alkanolamine Alkanolamine Formulation Solutions without Containing Quaternary Ammonium Hydroxides Quaternary Ammonium Hydroxide Copper Quaternary Copper Relative Etch rate Ammonium Etch rate Corrosion Alkanolamine wt. % (A/min.) Hydroxide wt. % (A/min.) Rate Monoethanolamine 9 9.8 Tetramethyl 0.45 9.8 1.0 Monoethanolamine 9 Tetramethyl 1.8 8.9 0.9 Monoethanolamine 9 Tetramethyl 5 6.8 0.7 Monoethanolamine 9 Tetramethyl 9 5.2 0.5 Monoethanolamine 9 Tetramethyl 13.5 4.8 0.5 Monoethanolamine 9 9.8 Tetrabutyl 0.9 10.0 1.0 Monoethanolamine 9 Tetrabutyl 5 9.7 1.0 Monoethanolamine 9 Tetrabutyl 13.5 5.7 0.6 Monoethanolamine 9 Tetrabutyl 23.3 4.4 0.4 Monoethanolamine 9 Tetrabutyl 41.4 4.2 0.4 1-Amino-2-propanol 11 7.7 Tetramethyl 1.1 7.4 1.0 1-Amino-2-propanol 11 Tetramethyl 2.2 7.5 1.0 1-Amino-2-propanol 11 Tetramethyl 6.1 6.9 0.9 1-Amino-2-propanol 11 Tetramethyl 11.0 5.1 0.7 2-(Methylamino)ethanol 11 9.0 Tetramethyl 1.1 7.8 0.9 2-(Methylamino)ethanol 11 Tetramethyl 2.2 7.0 0.8 2-(Methylamino)ethanol 11 Tetramethyl 6.1 6.5 0.7 2-(Methylamino)ethanol 11 Tetramethyl 11 6.8 0.7 Triethanolamine 22 5.1 Tetramethyl 2.2 5.4 1.0 Triethanolamine 22 Tetramethyl 4.4 4.7 0.9 Triethanolamine 22 Tetramethyl 12.2 3.4 0.7 - Cleaning solutions were evaluated for the ability to remove particles from wafers patterned with copper into a low-K organosilicon dielectric. These received a final copper chemical mechanical polish (CMP) using a Hitachi low pH barrier slurry followed by drying without post-CMP cleaning. Aqueous solutions of alkanolamines with and without added quaternary ammonium hydroxides similar to Examples 1 and 2 were prepared and diluted 30:1 with water. These diluted solutions were used to clean pieces of the dirty wafers described above. A single wafer spray tool operating at 150 rpm at room temperature for 60 seconds was used. Particle counts of 20×20 micron squares were obtained from scanning electron microscope images using the Object Count routine of Sigma Scan Pro software. The results, set forth in Table 3, clearly show the ability of quaternary ammonium hydroxides to enhance the particle removing ability of the alkanolamine solutions. Relative particle count=(particle count of formulation with quaternary ammonium hydroxide)÷(particle count of formulation without quaternary ammonium hydroxide).
-
TABLE 3 Effect of Quaternary Ammonium Hydroxides on Alkanolamine Cleaners Alkanolamine Formulation Comparative Alkanolamine Containing Solutions without Quaternary Ammonium Hydroxide Quaternary Ammonium Hydroxides Quaternary Particle Ammonium Particle Relative Alkanolamine wt. % Count Hydroxide wt. % Count Particle Count Monoethanolamine 0.3 14,400 Tetramethyl 0.02 5000 0.3 Monoethanolamine 0.3 Tetramethyl 0.03 860 0.06 Monoethanolamine 0.3 Tetramethyl 0.1 260 0.02 Monoethanolamine 0.3 Tetramethyl 0.2 260 0.02 Monoethanolamine 0.3 Tetramethyl 0.3 190 0.01 1-Amino-2-propanol 0.4 19,900 Tetramethyl 0.004 3400 0.2 1-Amino-2-propanol 0.4 Tetramethyl 0.01 1700 0.09 1-Amino-2-propanol 0.4 Tetramethyl 0.04 1800 0.09 1-Amino-2-propanol 0.4 Tetramethyl 0.07 660 0.03 2-(Methylamino)ethanol 0.4 3,800 Tetramethyl 0.004 2400 0.6 2-(Methylamino)ethanol 0.4 Tetramethyl 0.01 2200 0.6 2-(Methylamino)ethanol 0.4 Tetramethyl 0.07 880 0.2 2-(Methylamino)ethanol 0.4 Tetramethyl 0.2 100 0.03 Triethanolamine 0.7 28,000 Tetramethyl 0.04 8400 0.3 Triethanolamine 0.7 Tetramethyl 0.07 6100 0.2 Triethanolamine 0.7 Tetramethyl 0.1 5300 0.2 Triethanolamine 0.7 Tetramethyl 0.2 5200 0.2 - The usefulness of adding quaternary ammonium hydroxides to alkanolamine cleaning solutions was further demonstrated by comparing a quaternary ammonium hydroxide containing formulation to aqueous alkanolamine with and without an added known copper corrosion inhibitor, 1,2,4-triazole. Aqueous cleaning solutions were prepared for comparison and are listed in Table 4. These were evaluated for the ability to remove particles from wafers patterned with copper into a IOW-K organosilicon dielectric using the method described in Example 3. Additional (unpatterned) blanket copper wafer pieces were cleaned using these solutions under the same conditions, a single wafer spray tool operating at 150 rpm at room temperature for 60 seconds. After cleaning, surface roughness was evaluated using an atomic force microscope and the root mean square (Rms) roughness (in nanometers) of a 20×20 micron square determined. The results, set forth in Table 4, clearly show that quaternary ammonium hydroxide addition results in enhanced the particle removal and lower surface roughness than aqueous alkanolamine with or without the copper corrosion inhibitor.
-
TABLE 4 Comparison of Quaternary Ammonium Hydroxide and 1,2,4-Triazole Particle Rms Roughness Treatment Solution Count (nm) None 27,300 2.8 Monoethanolamine (0.3%) 10,500 2.7 Monoethanolamine (0.3%) 380 2.9 1,2,4-Triazole (0.003%) Monoethanolamine (0.3%) 200 1.7 Tetramethylammonium hydroxide (0.1%) - The utility of quaternary ammonium hydroxide-containing alkanolamine cleaning solutions was further demonstrated by using such a solution to strip a typical photoresist and anti-reflective coating (ARC) on a copper substrate. The test wafer was prepared by spin coating 0.2 micron of Brewer Science bottom-ARC #XL-20 onto a copper layer that had been deposited on a silicon wafer. The ARC was cured by baking at 190° C. followed by further spin coating with four microns of Shipley SPR-220 photoresist. The photoresist was then cured by baking at 140° C. followed by a one minute deep UV cure at the same temperature. Pieces of this wafer were stripped using a mixture of 92% monoethanolamine, 2% tetramethylammonium hydroxide, and 6% water under the following process conditions.
-
Temperature Time Run Number (° C.) (minutes) SEMs 1 70 30 FIG. 1 2 70 10 3 70 5 4 55 10 5 55 5 6 40 10 7 40 5 FIG. 2 - Scanning electron micrographs (SEM) were obtained for each wafer piece treated. These micrographs indicated that for every run listed above, the ARC and photoresist were completely removed without any damage to the underlying copper surface.
FIG. 1 illustrates the absence of any damage to the copper surface using most aggressive treatment. Further evidence of copper compatibility was obtained by measuring the copper etch rate of the formulation prepared above using the sheet resistance method described in Example 2. A copper etch rate of 4.3 Angstroms/minute at 70° C. was obtained which is similar to the improved etch rates reported for the formulations described in Example 2.FIG. 2 illustrates the complete removal of ARC and photoresist using the least aggressive treatment. - The utility of quaternary ammonium hydroxide-containing alkanolamine cleaning solutions was further demonstrated by stripping wafer pieces described in Example 5 using a mixture of 92% 2-(2-dimethylaminoethoxy)ethanol, 2% tetramethylammonium hydroxide, and 6% water under the following process conditions:
-
Temperature Time Run Number (° C.) (minutes) SEMs 1 70 60 FIG. 3 2 70 30 3 70 15 4 70 5 5 60 30 6 60 15 7 60 5 8 50 30 9 50 15 FIG. 4 10 50 5 - Scanning electron photomicrographs (SEMs) were obtained for each wafer piece treated. These micrographs indicated that for every run listed above, the ARC and photoresist were completely removed without any damage to the underlying copper surface.
FIG. 3 illustrates the absence of any damage to the copper surface using the most aggressive treatment. Further evidence of copper compatibility was obtained by measuring the copper etch rate of the formulation prepared above using the sheet resistance method described in Example 2. A favorably low copper etch rate of 2.4 Angstroms/minute at 70° C. was obtained.FIG. 4 illustrates the complete removal of ARC and photoresist using a much less aggressive treatment. - It has also been discovered that potassium hydroxide is an effective alternate to the quaternary ammonium hydroxide for use in an effective cleaning solution. Examples 7 and 8 set out below summarize data for compositions using an amine, (e.g. MEA), potassium hydroxide (KOH) and deionized water.
- Cleaning solutions were evaluated for the tendency to corrode copper. Aqueous solutions of an alkanolamine with and without added potassium hydroxide were prepared and evaluated using the method of Example 2. The results, set forth in Table 7, clearly show the ability of potassium hydroxide to prevent or moderate the copper corrosion (as measured by copper etch rate) that accompanies exposure to alkanolamines. Relative copper corrosion rate=(copper etch rate of formulation with potassium hydroxide)÷(copper etch rate of formulation without potassium hydroxide).
-
TABLE 7 Effect of Potassium Hydroxide on Alkanolamine Cleaners Comparative Alkanolamine Alkanolamine Formulation Solution without Containing Potassium Hydroxide Potassium Hydroxide Copper Potassium Copper Relative wt. Etch rate Hydroxide Etch rate Corrosion Alkanolamine % (A/min.) wt. % (A/min.) Rate Monoethanolamine 9 9.8 1.8 7.9 0.8 Monoethanolamine 9 5 6.5 0.7 Monoethanolamine 9 9 6.6 0.7 Monoethanolamine 9 13.5 5.1 0.5 - The usefulness of adding potassium hydroxide to alkanolamine cleaning solutions was further demonstrated by comparing a potassium hydroxide containing formulations to aqueous alkanolamines with no added potassium hydroxide. Aqueous cleaning solutions were prepared for comparison and are listed in Table 8. These were evaluated for the ability to remove particles from wafers patterned with copper into a low-K organosilicon dielectric using the method described in Example 3. The results, set forth in Table 8, clearly show that potassium hydroxide addition results in enhanced the particle removal.
-
TABLE 8 Particle Treatment Solution Count None 27,300 Monoethanolamine (0.3%) 10,500 Monoethanolamine (0.3%) 910 Potassium hydroxide (0.06%) Monoethanolamine (0.1%) 80 Potassium hydroxide (0.06%) - The foregoing examples illustrate the low corrosion rate and effective cleaning properties of compositions according to the invention.
- Additional short-loop patterned test wafers containing organosilicon glass (OSG) patterns on ECD copper and blanket ECD copper wafers were used in testing of the composition of the invention.
- A composition containing 9.0 wt % MEA, 5% TMAH, balance deionized water was used to clean a post etch device.
FIG. 5 is a pair of photomicrographs of the device prior to being exposed to the cleaning composition.FIG. 6 andFIG. 7 are photomicrographs of the device ofFIG. 5 after exposure to the cleaning composition for 10 minutes at 50° C. - In addition to copper, other metals have and will be used in the manufacture of microelectronic devices. Metals such as aluminum and tungsten would be exposed to cleaning solutions such as disclosed above. These cleaning solutions must not corrode the aluminum or tungsten or otherwise radically change the surface morphology. In order to demonstrate the efficacy of the above cleaning solution experiments were conducted using aluminum and tungsten. The results of those experiments are set forth in the following Examples 9 and 10.
- Cleaning solutions were evaluated for the tendency to corrode aluminum. Aqueous solutions of an alkanolamine (monoethanolamine) with and without an added quaternary ammonium hydroxide ([carboxymethyl]trimethylammonium hydroxide inner salt) were prepared:
-
Solution Components (Parts by Weight) A monoethanolamine (80) + water (20) B solution A + 0.6% (carboxymethyl)trimethylammonium hydroxide inner salt C monoethanolamine (40) + water (60) D solution C + 0.3% (carboxymethyl)trimethylammonium hydroxide inner salt - Identical blanket aluminum (containing 0.5% copper) on silicon wafer pieces were submersed in stirred solutions A and B for 10 minutes at 65° C. Four point probe measurements for sheet resistance were made on these pieces prior to and after treatment. Aluminum etch rates (in Angstroms per minute) for the solutions were calculated:
- Coupons of 99.8% aluminum (0.05×12×40 mm) were cleaned in water, isopropanol, dried and weighed. Coupons were heated in solutions C and D for 3 hours at 65° C., the coupons were removed, rinsed with water, isopropanol, dried and reweighed. Weight losses were converted to the following corrosion rates:
- The results show the ability of a quaternary ammonium hydroxides to moderate aluminum corrosion that accompanies exposure to alkanolamines.
- Cleaning solutions were evaluated for the tendency to corrode tungsten. Aqueous solutions of alkanolamines corrode tungsten very slowly making the etch rates difficult to measure. Adding a dipolar aprotic solvent, in this case N,N-dimethylacetamide, increases corrosion rates to a measurable range. The following alkanolamine (monoethanolamine) solutions with and without an added quaternary ammonium hydroxide (tetramethylammonium hydroxide) were prepared:
-
Solution Components (Parts by Weight) E N,N-dimethylacetamide (89) + monoethanolamine (9) + water (2) F solution E + 0.5% tetramethylammonium hydroxide - Coupons of 99.9+% tungsten (0.05×10×24 mm) were cleaned in water, then acetone, dried and weighed. Coupons were heated in solutions E and F for 5 hours at 85° C., the coupons were removed, rinsed with water, then acetone, dried and reweighed. Weight losses were converted to the following corrosion rates:
- The results show the ability of a quaternary ammonium hydroxides to moderate tungsten corrosion that accompanies exposure to alkanolamines.
- From the foregoing examples it is evident that cleaning solutions according to the invention described herein will not only clean but have little adverse effects on exposed aluminum or tungsten surfaces on a microelectronic device.
- Although the invention is illustrated and described herein with reference to specific embodiments, the invention is not intended to be limited to the details shown. Rather, various modifications may be made in the details within the scope and range of equivalents of the claims without departing from the invention.
Claims (11)
1.-11. (canceled)
12. A cleaning composition consisting essentially of 0.30 to 9.0 wt % alkanolamine, 0.06 to 13.5 wt % potassium hydroxide, balance water.
13. The cleaning composition of claim 12 , wherein the alkanolamine comprises a species selected from the group consisting of monoethanolamine, 1-amino-2 propanol, 2-(methylamino) ethanol, triethanolamine, and mixtures thereof.
14. The cleaning composition of claim 12 , wherein the alkanolamine comprises monoethanolamine.
15. A method for preparing a post-CMP cleaning solution containing 0.02 to 13.5 wt % quaternary ammonium hydroxide, 0.3 to 22.0% by weight alkanolamine, balance water, said method comprising the steps of:
a) mixing 100% of the water and said alkanolamine;
b) adding said quaternary ammonium hydroxide to said water-alkanolamine mixture and mixing with low shear conditions to achieve a final mixture; and
c) filtering said final mixture through a 0.1 micron filter.
16. The method of claim 15 , wherein the mixing with low shear conditions is carried out for about 10 min.
17. The method of claim 15 , wherein the alkanolamine comprises a species selected from the group consisting of monoethanolamine, 1-amino-2 propanol, 2-(methylamino) ethanol; triethanolamine and mixtures thereof.
18. The method of claim 15 , wherein the quaternary ammonium hydroxide comprises a species selected from the group consisting of tetramethyl ammonium hydroxide, tetrabutyl ammonium hydroxide and mixtures thereof.
19. The method of claim 15 , wherein the alkanolamine comprises monoethanolamine and wherein the quaternary ammonium hydroxide comprises (carboxymethyl) trimethylammonium hydroxide inner salt.
20. The method of claim 15 , wherein the alkanolamine comprises monoethanolamine and wherein the quaternary ammonium hydroxide comprises tetramethylammonium hydroxide.
21. A cleaning composition including 2-(2-dimethylaminoethoxy)ethanol, tetramethylammonium hydroxide, and water.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US12/111,469 US20080200361A1 (en) | 2005-03-30 | 2008-04-29 | Aqueous cleaner with low metal etch rate |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/094,113 US7365045B2 (en) | 2005-03-30 | 2005-03-30 | Aqueous cleaner with low metal etch rate comprising alkanolamine and tetraalkylammonium hydroxide |
US12/111,469 US20080200361A1 (en) | 2005-03-30 | 2008-04-29 | Aqueous cleaner with low metal etch rate |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US11/094,113 Continuation US7365045B2 (en) | 2005-03-30 | 2005-03-30 | Aqueous cleaner with low metal etch rate comprising alkanolamine and tetraalkylammonium hydroxide |
Publications (1)
Publication Number | Publication Date |
---|---|
US20080200361A1 true US20080200361A1 (en) | 2008-08-21 |
Family
ID=36603314
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US11/094,113 Active 2025-05-22 US7365045B2 (en) | 2005-03-30 | 2005-03-30 | Aqueous cleaner with low metal etch rate comprising alkanolamine and tetraalkylammonium hydroxide |
US12/111,469 Abandoned US20080200361A1 (en) | 2005-03-30 | 2008-04-29 | Aqueous cleaner with low metal etch rate |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US11/094,113 Active 2025-05-22 US7365045B2 (en) | 2005-03-30 | 2005-03-30 | Aqueous cleaner with low metal etch rate comprising alkanolamine and tetraalkylammonium hydroxide |
Country Status (3)
Country | Link |
---|---|
US (2) | US7365045B2 (en) |
TW (1) | TW200706647A (en) |
WO (1) | WO2006107475A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20070093065A1 (en) * | 2005-10-25 | 2007-04-26 | Oki Electric Industry Co., Ltd. | Method for manufacturing a semiconductor wafer |
US20100160200A1 (en) * | 2008-03-19 | 2010-06-24 | Fujifilm Corporation | Cleaning liquid for semiconductor device and cleaning method |
Families Citing this family (33)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
EP1891482B1 (en) | 2005-06-07 | 2014-04-30 | Advanced Technology Materials, Inc. | Metal and dielectric compatible sacrificial anti-reflective coating cleaning and removal composition |
TW200734448A (en) * | 2006-02-03 | 2007-09-16 | Advanced Tech Materials | Low pH post-CMP residue removal composition and method of use |
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 |
US20100112728A1 (en) * | 2007-03-31 | 2010-05-06 | Advanced Technology Materials, Inc. | Methods for stripping material for wafer reclamation |
TWI437093B (en) * | 2007-08-03 | 2014-05-11 | Epoch Material Co Ltd | Aqueous cleaning composition for semiconductor copper processing |
CN101362986B (en) * | 2007-08-08 | 2012-09-05 | 长兴开发科技股份有限公司 | Aqueous cleaning compositions for semi-conductor copper processing |
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 |
CN101226346B (en) * | 2007-12-27 | 2010-06-09 | 周伟 | Demoundiing technique of photoresist as well as a first composition, a second composition and demoulding agent water solution used in said technique |
JP5873718B2 (en) | 2008-10-21 | 2016-03-01 | 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 | Copper cleaning and protection compound |
US8298751B2 (en) * | 2009-11-02 | 2012-10-30 | International Business Machines Corporation | Alkaline rinse agents for use in lithographic patterning |
SI2348142T1 (en) | 2010-01-25 | 2019-03-29 | Westinghouse Electric Company Llc | Method and composition for removing scale deposits formed on a metal surface within a steam generating system |
TWI513815B (en) | 2010-01-29 | 2015-12-21 | Entegris Inc | Cleaning agent for semiconductor provided with metal wiring |
CN105304485B (en) | 2010-10-06 | 2019-02-12 | 恩特格里斯公司 | The composition and method of selective etch metal nitride |
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 |
US10176979B2 (en) | 2012-02-15 | 2019-01-08 | Entegris, Inc. | Post-CMP removal using compositions and method of use |
KR20150016574A (en) | 2012-05-18 | 2015-02-12 | 인티그리스, 인코포레이티드 | Composition and process for stripping photoresist from a surface including titanium nitride |
KR102118964B1 (en) | 2012-12-05 | 2020-06-08 | 엔테그리스, 아이엔씨. | Compositions for cleaning iii-v semiconductor materials and methods of using same |
EP2964725B1 (en) | 2013-03-04 | 2021-06-23 | Entegris, Inc. | Compositions and methods for selectively etching titanium nitride |
JP6203525B2 (en) * | 2013-04-19 | 2017-09-27 | 関東化學株式会社 | Cleaning liquid composition |
JP6723152B2 (en) | 2013-06-06 | 2020-07-15 | インテグリス・インコーポレーテッド | 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 |
WO2015031620A1 (en) | 2013-08-30 | 2015-03-05 | Advanced Technology Materials, Inc. | Compositions and methods for selectively etching titanium nitride |
EP3077129B1 (en) | 2013-12-06 | 2020-11-11 | FujiFilm Electronic Materials USA, Inc. | Cleaning formulation for removing residues on surfaces |
WO2015095175A1 (en) | 2013-12-16 | 2015-06-25 | Advanced Technology Materials, Inc. | Ni:nige:ge selective etch formulations and method of using same |
SG11201605003WA (en) | 2013-12-20 | 2016-07-28 | Entegris Inc | Use of non-oxidizing strong acids for the removal of ion-implanted resist |
US10475658B2 (en) | 2013-12-31 | 2019-11-12 | Entegris, 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 |
US11127587B2 (en) | 2014-02-05 | 2021-09-21 | Entegris, Inc. | Non-amine post-CMP compositions and method of use |
KR20200138742A (en) | 2018-03-28 | 2020-12-10 | 후지필름 일렉트로닉 머티리얼스 유.에스.에이., 아이엔씨. | Cleaning composition |
WO2024053647A1 (en) * | 2022-09-06 | 2024-03-14 | 花王株式会社 | Substrate processing method |
Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4808513A (en) * | 1987-04-06 | 1989-02-28 | Morton Thiokol, Inc. | Method of developing a high contrast, positive photoresist using a developer containing alkanolamine |
US5849467A (en) * | 1996-01-29 | 1998-12-15 | Tokyo Ohka Kogyo Co., Ltd. | Method for the pre-treatment of a photoresist layer on a substrate surface |
US6194366B1 (en) * | 1999-11-16 | 2001-02-27 | Esc, Inc. | Post chemical-mechanical planarization (CMP) cleaning composition |
US6417147B2 (en) * | 2000-02-29 | 2002-07-09 | Showa Denko K.K. | Cleaning agent composition, method for cleaning and use thereof |
US6492308B1 (en) * | 1999-11-16 | 2002-12-10 | Esc, Inc. | Post chemical-mechanical planarization (CMP) cleaning composition |
US6627587B2 (en) * | 2001-04-19 | 2003-09-30 | Esc Inc. | Cleaning compositions |
US6723691B2 (en) * | 1999-11-16 | 2004-04-20 | Advanced Technology Materials, Inc. | Post chemical-mechanical planarization (CMP) cleaning composition |
US7005382B2 (en) * | 2002-10-31 | 2006-02-28 | Jsr Corporation | Aqueous dispersion for chemical mechanical polishing, chemical mechanical polishing process, production process of semiconductor device and material for preparing an aqueous dispersion for chemical mechanical polishing |
US20060166847A1 (en) * | 2005-01-27 | 2006-07-27 | Advanced Technology Materials, Inc. | Compositions for processing of semiconductor substrates |
US20070007248A1 (en) * | 2004-02-27 | 2007-01-11 | Lane Sarah J | Compositions and methods for chemical mechanical polishing silica and silicon nitride |
US7291280B2 (en) * | 2004-12-28 | 2007-11-06 | Rohm And Haas Electronic Materials Cmp Holdings, Inc. | Multi-step methods for chemical mechanical polishing silicon dioxide and silicon nitride |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5143648A (en) * | 1989-07-20 | 1992-09-01 | Nippon Hypox Laboratories Incorporated | Ascorbic acid derivative and use as antioxidant |
US6326130B1 (en) | 1993-10-07 | 2001-12-04 | Mallinckrodt Baker, Inc. | Photoresist strippers containing reducing agents to reduce metal corrosion |
US5466389A (en) * | 1994-04-20 | 1995-11-14 | J. T. Baker Inc. | PH adjusted nonionic surfactant-containing alkaline cleaner composition for cleaning microelectronics substrates |
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 |
KR100360394B1 (en) * | 1995-12-20 | 2003-01-24 | 삼성전자 주식회사 | Method for cleaning semiconductor substrate and cleaning solution used for the same |
US5709756A (en) * | 1996-11-05 | 1998-01-20 | Ashland Inc. | Basic stripping and cleaning composition |
MY131912A (en) * | 2001-07-09 | 2007-09-28 | Avantor Performance Mat Inc | Ammonia-free alkaline microelectronic cleaning compositions with improved substrate compatibility |
US9217929B2 (en) * | 2004-07-22 | 2015-12-22 | Air Products And Chemicals, Inc. | Composition for removing photoresist and/or etching residue from a substrate and use thereof |
US8263539B2 (en) * | 2005-10-28 | 2012-09-11 | Dynaloy, Llc | Dynamic multi-purpose composition for the removal of photoresists and methods for its use |
-
2005
- 2005-03-30 US US11/094,113 patent/US7365045B2/en active Active
-
2006
- 2006-03-02 WO PCT/US2006/007676 patent/WO2006107475A1/en active Application Filing
- 2006-03-28 TW TW095110660A patent/TW200706647A/en unknown
-
2008
- 2008-04-29 US US12/111,469 patent/US20080200361A1/en not_active Abandoned
Patent Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4808513A (en) * | 1987-04-06 | 1989-02-28 | Morton Thiokol, Inc. | Method of developing a high contrast, positive photoresist using a developer containing alkanolamine |
US5849467A (en) * | 1996-01-29 | 1998-12-15 | Tokyo Ohka Kogyo Co., Ltd. | Method for the pre-treatment of a photoresist layer on a substrate surface |
US6194366B1 (en) * | 1999-11-16 | 2001-02-27 | Esc, Inc. | Post chemical-mechanical planarization (CMP) cleaning composition |
US6492308B1 (en) * | 1999-11-16 | 2002-12-10 | Esc, Inc. | Post chemical-mechanical planarization (CMP) cleaning composition |
US6723691B2 (en) * | 1999-11-16 | 2004-04-20 | Advanced Technology Materials, Inc. | Post chemical-mechanical planarization (CMP) cleaning composition |
US6417147B2 (en) * | 2000-02-29 | 2002-07-09 | Showa Denko K.K. | Cleaning agent composition, method for cleaning and use thereof |
US6627587B2 (en) * | 2001-04-19 | 2003-09-30 | Esc Inc. | Cleaning compositions |
US6851432B2 (en) * | 2001-04-19 | 2005-02-08 | Advanced Technology Materials, Inc. | Cleaning compositions |
US7005382B2 (en) * | 2002-10-31 | 2006-02-28 | Jsr Corporation | Aqueous dispersion for chemical mechanical polishing, chemical mechanical polishing process, production process of semiconductor device and material for preparing an aqueous dispersion for chemical mechanical polishing |
US20070007248A1 (en) * | 2004-02-27 | 2007-01-11 | Lane Sarah J | Compositions and methods for chemical mechanical polishing silica and silicon nitride |
US7291280B2 (en) * | 2004-12-28 | 2007-11-06 | Rohm And Haas Electronic Materials Cmp Holdings, Inc. | Multi-step methods for chemical mechanical polishing silicon dioxide and silicon nitride |
US20060166847A1 (en) * | 2005-01-27 | 2006-07-27 | Advanced Technology Materials, Inc. | Compositions for processing of semiconductor substrates |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20070093065A1 (en) * | 2005-10-25 | 2007-04-26 | Oki Electric Industry Co., Ltd. | Method for manufacturing a semiconductor wafer |
US20100160200A1 (en) * | 2008-03-19 | 2010-06-24 | Fujifilm Corporation | Cleaning liquid for semiconductor device and cleaning method |
US7888300B2 (en) * | 2008-03-19 | 2011-02-15 | Fujifilm Corporation | Cleaning liquid for semiconductor device and cleaning method |
Also Published As
Publication number | Publication date |
---|---|
TW200706647A (en) | 2007-02-16 |
WO2006107475A1 (en) | 2006-10-12 |
US20060229221A1 (en) | 2006-10-12 |
US7365045B2 (en) | 2008-04-29 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US7365045B2 (en) | Aqueous cleaner with low metal etch rate comprising alkanolamine and tetraalkylammonium hydroxide | |
JP4942275B2 (en) | Cleaning composition after chemical mechanical planarization (CMP) | |
EP1360712B1 (en) | Post chemical-mechanical planarization (cmp) cleaning composition | |
US6194366B1 (en) | Post chemical-mechanical planarization (CMP) cleaning composition | |
EP1888735B1 (en) | Copper passivating post-chemical mechanical polishing cleaning composition and method of use | |
US7922823B2 (en) | Compositions for processing of semiconductor substrates | |
US20060148666A1 (en) | Aqueous cleaner with low metal etch rate | |
US20080076688A1 (en) | Copper passivating post-chemical mechanical polishing cleaning composition and method of use | |
TWI460268B (en) | Semiconductor substrate cleaning solution composition | |
JP2002543272A (en) | Composition for cleaning organic and plasma-etched residues for semiconductor devices | |
EP3599633B1 (en) | Post etch residue cleaning compositions and methods of using the same | |
KR20100011950A (en) | Cleaning compositions with very low dielectric etch rates | |
EP2687589A2 (en) | Copper passivating post-chemical mechanical polishing cleaning composition and method of use |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |