TWI445816B - Alkaline aqueous solution composition for substrate cleaning or etching - Google Patents
Alkaline aqueous solution composition for substrate cleaning or etching Download PDFInfo
- Publication number
- TWI445816B TWI445816B TW097121237A TW97121237A TWI445816B TW I445816 B TWI445816 B TW I445816B TW 097121237 A TW097121237 A TW 097121237A TW 97121237 A TW97121237 A TW 97121237A TW I445816 B TWI445816 B TW I445816B
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- Prior art keywords
- aqueous solution
- solution composition
- etching
- concentration
- cleaning
- Prior art date
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- 239000007864 aqueous solution Substances 0.000 title claims description 40
- 239000000203 mixture Substances 0.000 title claims description 39
- 238000004140 cleaning Methods 0.000 title claims description 36
- 239000000758 substrate Substances 0.000 title claims description 31
- 238000005530 etching Methods 0.000 title claims description 25
- 239000002738 chelating agent Substances 0.000 claims description 35
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 229910052751 metal Inorganic materials 0.000 claims description 26
- 239000002184 metal Substances 0.000 claims description 26
- 229910052757 nitrogen Inorganic materials 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 19
- 125000004429 atom Chemical group 0.000 claims description 16
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical group [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- 229910052715 tantalum Inorganic materials 0.000 claims description 12
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 11
- -1 cyano, hydroxy, decyl Chemical group 0.000 claims description 8
- 239000011521 glass Substances 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 125000002030 1,2-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([*:2])C([H])=C1[H] 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- 125000006374 C2-C10 alkenyl group Chemical group 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000000304 alkynyl group Chemical group 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 239000013522 chelant Substances 0.000 claims description 2
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 description 22
- 239000004065 semiconductor Substances 0.000 description 22
- 230000000694 effects Effects 0.000 description 17
- 239000007788 liquid Substances 0.000 description 14
- 239000012535 impurity Substances 0.000 description 12
- 229910052759 nickel Inorganic materials 0.000 description 10
- 229910052742 iron Inorganic materials 0.000 description 8
- 238000001179 sorption measurement Methods 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 6
- 229910052707 ruthenium Inorganic materials 0.000 description 6
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 5
- 239000012670 alkaline solution Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 239000003112 inhibitor Substances 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000011109 contamination Methods 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 150000007530 organic bases Chemical class 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229960003330 pentetic acid Drugs 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 238000004876 x-ray fluorescence Methods 0.000 description 2
- CCUNBJAVKGOAEV-UHFFFAOYSA-N 2,2-dihydroxy-2-phenylacetic acid;ethane-1,2-diamine Chemical compound NCCN.OC(=O)C(O)(O)C1=CC=CC=C1 CCUNBJAVKGOAEV-UHFFFAOYSA-N 0.000 description 1
- KIZQNNOULOCVDM-UHFFFAOYSA-M 2-hydroxyethyl(trimethyl)azanium;hydroxide Chemical compound [OH-].C[N+](C)(C)CCO KIZQNNOULOCVDM-UHFFFAOYSA-M 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229940074391 gallic acid Drugs 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- XKUKSGPZAADMRA-UHFFFAOYSA-N glycyl-glycyl-glycine Natural products NCC(=O)NCC(=O)NCC(O)=O XKUKSGPZAADMRA-UHFFFAOYSA-N 0.000 description 1
- 108010067216 glycyl-glycyl-glycine Proteins 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002908 osmium compounds Chemical class 0.000 description 1
- PTMHPRAIXMAOOB-UHFFFAOYSA-N phosphoramidic acid Chemical class NP(O)(O)=O PTMHPRAIXMAOOB-UHFFFAOYSA-N 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 150000003481 tantalum Chemical class 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 150000003567 thiocyanates Chemical class 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/02—Etching, surface-brightening or pickling compositions containing an alkali metal hydroxide
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C15/00—Surface treatment of glass, not in the form of fibres or filaments, by etching
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
- C03C23/0075—Cleaning of glass
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
- C09K13/06—Etching, surface-brightening or pickling compositions containing an inorganic acid with organic material
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/044—Hydroxides or bases
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/30—Amines; Substituted amines ; Quaternized amines
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02002—Preparing wafers
- H01L21/02005—Preparing bulk and homogeneous wafers
- H01L21/02008—Multistep processes
- H01L21/0201—Specific process step
- H01L21/02019—Chemical etching
-
- 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
- H01L21/02043—Cleaning before device manufacture, i.e. Begin-Of-Line process
- H01L21/02052—Wet cleaning only
-
- 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
-
- 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
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/30604—Chemical etching
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/14—Hard surfaces
- C11D2111/22—Electronic devices, e.g. PCBs or semiconductors
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Geochemistry & Mineralogy (AREA)
- Inorganic Chemistry (AREA)
- Cleaning Or Drying Semiconductors (AREA)
- Detergent Compositions (AREA)
- Weting (AREA)
Description
本發明係關於一種鹼性水溶液組成物,其用於基板洗淨或蝕刻。更詳言之,係關於一種鹼性水溶液組成物,其為於使用鹼性水溶液之洗淨及蝕刻步驟(其施行於用以製造半導體之矽晶圓製造步驟、半導體元件(device)製造步驟及其他電子元件製造步驟中)中,為了防止鹼性水溶液中之金屬雜質附著於基板表面、且更加以洗淨去除者。
於用以製造半導體之矽晶圓製造步驟中,將晶圓從單晶矽晶錠(ingot)中切出、加工至規定之厚度時,為了達到均勻蝕刻之目的,用氫氧化鈉或氫氧化鉀進行蝕刻。此時,含於氫氧化鈉或氫氧化鉀中之金屬雜質大量吸附於晶圓表面。通常於其之後,利用稀氫氟酸等酸洗淨去除,但特別是於低電阻基板中,Cu或Ni容易擴散至內部,其中,由於Ni於氫氧化鈉溶液的使用溫度亦即80℃左右會擴散,因此藉由酸所進行的表面洗淨,並無法去除擴散至內部之金屬雜質而成為問題。
再者,實際上除了Cu或Ni以外,Fe等過渡金屬大量吸附於矽晶圓表面,必須用酸性洗淨液等加以洗淨去除,所以產生半導體製造工程冗長、複雜化,成本升高或生產率低下等問題。
又,於製造矽晶圓之最終步驟或半導體元件製造步驟
中,特別是以去除粒子為目的,而使用鹼性洗淨液。例如於電晶體製造步驟(Front End of Line)中,經常使用氨及過氧化氫之混合液,亦即SC-1洗淨液。又,於配線步驟,亦即CMP(化學機械研磨)後之洗淨步驟中,使用如氫氧化四甲基銨之有機鹼。雖然這些洗淨液於構成成分中不含金屬,但即使於此場合中,仍有含於洗淨液中之金屬雜質或來自前面步驟之相當少量之金屬雜質吸附於晶圓表面而有影響電子特性之虞。
如上所述,由於鹼性洗淨液無洗淨金屬雜質之能力、或反而使其更容易吸附於基板表面,所以一般的洗淨製程是將鹼性洗淨液與能夠洗淨金屬雜質之酸性洗淨液組合。
於此,上述SC-1洗淨液係與鹽酸與過氧化氫之水溶液亦即SC-2洗淨液、或稀氫氟酸搭配使用。此洗淨製程約佔半導體製造製程的3分之1,由於其全部使用鹼性洗淨液及酸性洗淨液之2種液體來施行,所以產生半導體製造工程冗長、複雜化,成本升高或生產率低下等問題。
又,於製造大容量記憶裝置亦即硬碟中,以往認為微粒子污染是問題,但到目前為止並不認為金屬污染是問題,而藉由鹼及酸來進行洗淨。但是,現已了解到玻璃基板會被鹼性洗淨液中之金屬雜質污染,結果將會引起粒子污染,而產生與矽基板相同之問題。
因此,為了防止金屬雜質於鹼性水溶液中之吸附,有提案使用各種錯合劑(螯合劑)。作為螯合劑,如乙二胺四乙酸(EDTA)或二乙烯三胺五乙酸(DTPA)這樣的胺基羧酸
類,在很久以前即為已知;於半導體製造領域亦有此提案(專利文獻1及2),但螯合劑化合物不安定,效果還不夠好。
除此之外,亦有提案使用胺基膦酸類(專利文獻3)、縮合磷酸類(專利文獻4)、硫氰酸鹽(專利文獻5)、亞硝酸離子及硝酸離子(專利文獻6)等螯合劑。但是,由於這些螯合劑,是用於SC-1洗淨液中者,所以雖然於如氨這類的較弱的鹼性溶液中有效果,但於如氫氧化鈉或氫氧化四甲基銨這類的強鹼性水溶液中則無效。
又,近年來提案中之有效果者,有以乙二胺二鄰羥基苯乙酸作為螯合劑者(專利文獻7),雖然此螯合劑比起EDTA等一般螯合劑有較佳效果,但仍達不到半導體或矽晶圓製造業者要求之防止金屬吸附之水準。
再者,作為螯合劑以外之方法,有提出使鋁溶解之方法(專利文獻8)、使矽或矽化合物溶解之方法(專利文獻9)等,但由於鋁或矽等之溶解很麻煩且花時間,而產生成本升高或生產率低下等問題。
[專利文獻1]日本專利公報特開2005-310845
[專利文獻2]日本專利公報特開2006-165408
[專利文獻3]日本特許第3503326號公報
[專利文獻4]日本特許第3274834號公報
[專利文獻5]日本專利公報特開2005-038969
[專利文獻6]日本專利公報特開2005-210085
[專利文獻7]日本特許第3198878號公報
[專利文獻8]日本專利公報特開2005-158759
[專利文獻9]日本專利公報特開平09-129624
因此,本發明係以提供一種鹼性水溶液組成物為目的,其係於使用強鹼性水溶液的半導體基板或玻璃基板之蝕刻或洗淨步驟中,防止金屬吸附於基板表面,且更進行洗淨加以去除,來提高半導體元件等之電子特性,且能夠有助於生產率之提高者。
本發明者們為解決上述問題而經深入鑽研,結果發現某特定有機化合物可解決上述問題,有效防止金屬吸附於基板上,於更進一步研究之後,遂完成本發明。
亦即,本發明係關於一種鹼性水溶液組成物,其係用於基板洗淨或蝕刻之鹼性水溶液組成物,其中含有結構式(1)表示之螯合劑及鹼性成分;
式中:R為C2-6
伸烷基、1,2-環己烯基或1,2-伸苯基,其中R的任意1或2個以上之氫原子亦可被相同或不同的取代基取代;A環及B環為苯環,其中任意1或2個以上之氫原子亦可被相同或不同的取代基取代;於此,取代基為由C1-10
烷基、C2-10
烯基、C2-10
炔基、C1-10
醯基、C1-10
烷氧基、苯基、苄基、萘基、羧基、磺酸基、氰基、羥基、巰基、胺基、鹵素及硝基所組成之群中選出。
又,關於上述鹼性水溶液組成物,其中螯合劑為N,N’-雙(亞柳基)-1,2-乙二胺、N,N’-雙(亞柳基)-1,2-丙二胺或N,N’-雙(亞柳基)-1,3-丙二胺。
再者,關於上述鹼性水溶液組成物,其中鹼性成分為氫氧化四甲基銨。
又,關於上述鹼性水溶液組成物,其中鹼性成分為氫氧化鈉及/或氫氧化鉀。
再者,關於上述鹼性水溶液組成物,其中更含有其他螯合劑。
又,關於上述鹼性水溶液組成物,其係用於洗淨液,其中鹼性成分的濃度為0.01~1.0wt%、螯合劑的濃度為0.0005~1.0wt%。
再者,關於上述鹼性水溶液組成物,其中更含有防蝕劑。
又,關於上述鹼性水溶液組成物,其中更含有界面活
性劑。
再者,關於上述鹼性水溶液組成物,其係用於蝕刻液,其中鹼性成分的濃度為1.0~50wt%、螯合劑的濃度為0.001~5.0wt%。
又,關於上述鹼性水溶液組成物,其中基板為矽晶圓,且於洗淨或蝕刻後該矽晶圓表面的Ni濃度變成20×1010
atoms/cm2
以下。
再者,關於一種基板洗淨或蝕刻方法,係用上述鹼性水溶液組成物,將基板洗淨或蝕刻,使該基板表面的Ni濃度在20×1010
atoms/cm2
以下。
本發明之鹼性水溶液組成物為強鹼性溶液且同時對於防止Ni等金屬雜質吸附於基板表面極為有效,但其機構未必完全明白。
於此,可認為含於本發明水溶液組成物的結構式(1)表示之螯合劑,是分子內四牙配位子,且其與Ni等金屬形成如下所示之螯合構造。
如上所述,本發明的結構式(1)表示之螯合劑,可認為
係藉由官能基R的長度、官能基R的柔軟性、甲亞胺鍵結的配位原子N及酚性羥基的配位原子O的位置關係,而與Ni等特定金屬離子於理想的位置上發生配位鍵結。再者,可認為由於有甲亞胺鍵結,錯合體才堅固、平面性強,容易形成二聚物。藉由這些理由,可認為即使於強鹼溶液中,其會形成極為安定且堅固的螯合環,比起其他螯合劑,可非常有效率地防止金屬雜質吸附於基板表面。
因此可認為本發明的結構式(1)表示之螯合劑中,分子構造中官能基R的長度、官能基R的柔軟性、甲亞胺鍵結及甲亞胺鍵結的配位原子N與酚性羥基的配位原子O的位置關係特別重要。
於使用鹼性溶液之蝕刻步驟中,藉由本發明之鹼性水溶液組成物,變得能夠抑制Ni吸附於矽晶圓表面之量於20×1010
atoms/cm2
以下,此為於習知一般半導體製造步驟等中無法達到者。
又,於使用鹼性洗淨液之洗淨步驟中,由於能夠防止金屬雜質吸附,且加以洗淨去除之,所以能夠省略酸性洗淨,而大幅縮短約佔半導體製造步驟1/3之洗淨步驟、能夠降低成本及提高生產率。
以下詳細地說明本發明。本發明之鹼性水溶液組成物,是在製造半導體及其他電子元件中,以洗淨或蝕刻為目的所使用之水溶液組成物,且含有螯合劑及鹼性成分等者。
又,使用本發明之水溶液組成物來進行洗淨或蝕刻之基板,是矽晶圓、其他半導體基板(此兩者為用於製造半導體及其他電子設備)、及用於平面顯示器與硬碟之玻璃基板等。
作為用於本發明之防止金屬吸附之螯合劑,是結構式(1)表示之螯合劑,以於此結構式(1)中的官能基R為C2-4
之伸烷基之螯合劑為佳,以於此結構式(1)中的官能基R為C2
或C3
之伸烷基之螯合劑為特佳。
具體化合物可舉例:N,N’-雙(亞柳基)-1,2-乙二胺、N,N’-雙(亞柳基)-1,2-丙二胺、N,N’-雙(亞柳基)-1,3-丙二胺、N,N’-雙(亞柳基)-1,4-丁二胺、N,N’-雙(亞柳基)-1,6-己二胺、N,N’-雙(亞柳基)-1,2-苯二胺等;以N,N’-雙(亞柳基)-1,2-乙二胺、N,N’-雙(亞柳基)-1,2-丙二胺、N,N’-雙(亞柳基)-1,3-丙二胺、N,N’-雙(亞柳基)-1,4-丁二胺等為佳,以N,N’-雙(亞柳基)-1,2-乙二胺、N,N’-雙(亞柳基)-1,2-丙二胺、N,N’-雙(亞柳基)-1,3-丙二胺等為特佳。
只要有充分的效果,則不特別限制這些螯合劑之濃度,係由鹼濃度與效果綜合判斷來決定。自能夠配合使用目的來發揮充分效果、得到與螯合劑濃度成比例之效果、以及能夠不析出而安定保存等觀點,來進行考慮。
使用螯合劑之濃度,於作為洗淨液使用之情形中,以0.0005~1.0wt%為佳,以0.001~0.5wt%為較佳,以0.005~0.1wt%為更佳。
又,於作為蝕刻液使用的情形中,以0.001~5.0wt%為佳,以0.01~1.0wt%為較佳,以0.05~0.5wt%為更佳。
作為用於本發明之鹼性成分,只要是於製造半導體及其他電子元件中,用於蝕刻或洗淨之鹼性成分,則不特別限制之,可舉例如:氫氧化鈉、氫氧化鉀等無機鹼;氫氧化四甲基銨、氫氧化三甲基(羥基乙基)銨等有機鹼;氨等。
以氫氧化鈉、氫氧化鉀及氫氧化四甲基銨為特佳。
只要有充分的效果,則不特別限制這些鹼性成分之濃度,其隨著作為處理液之使用目的而大有不同。於作為蝕刻液使用的情況中,配合目的,使用1wt%~50wt%之廣泛的濃度。
於洗淨液的情形中,考慮到充分洗淨效果及防止對基板造成傷害,以0.01wt%~1.0wt%為佳,以0.05wt%~0.8wt%為較佳,以0.1wt%~0.5wt%為更佳。
又,螯合劑有對金屬之特異性,數種螯合劑並用對於防止廣泛的金屬吸附或洗淨有效。因此,本發明亦可更含有其他螯合劑。
作為用於本發明之其他螯合劑,只要是於製造半導體及其他電子元件中,用於蝕刻或洗淨之螯合劑,則不特別限制之,可舉例如:乙二胺四乙酸、三甘胺酸(nitrilotriacetic acid)等胺基羧酸類;檸檬酸、酒石酸等有機酸類;啡啉等含氮雜環化合物等。以乙二胺四乙酸為特佳,因為其與廣泛的金屬形成錯合體。
作為使用之濃度,只要有充分的效果,則不特別限制之,考慮到發揮充分效果與保存時之安定性等,以0.001~1wt%為佳,以0.01~0.5wt%為更佳。
又,於配線步驟亦即CMP(化學機械研磨)後之洗淨步驟中,於將本發明作為洗淨液使用的情形中,為了防止由於其與鋁或銅等配線材料接觸而導致配線材料腐蝕,亦可更含有防蝕劑。
作為用於本發明之防蝕劑,只要是於製造半導體及其他電子元件中,用於處理基板之防蝕劑,則不特別限制之,可使用一般鋁或銅之防蝕劑。作為鋁之防蝕劑,可舉例如:糖類(如山梨糖醇)、鄰苯二酚、有酚性羥基之化合物(如沒食子酸)、有羧基之高分子化合物(如聚丙烯酸)等;作為銅之防蝕劑,可舉例如苯并三唑等之雜環化合物或硫脲等。以苯并三唑為特佳。
作為使用之濃度,只要有充分的效果則不特別限制之,考慮到發揮充分效果與保存時之安定性等,以0.01~5wt%為佳,以0.05~2wt%為更佳。
又,於配線步驟亦即CMP(化學機械研磨)後之洗淨步驟中,將本發明作為洗淨液使用的情形中,為了改善其與絕緣膜之潤濕性(Wettability),亦可更含有界面活性劑。
作為用於本發明之界面活性劑,只要是於製造半導體及其他電子元件中,用於處理基板之界面活性劑,則不特別限制之,但以非離子型界面活性劑為佳,以聚氧化烯烷醚及聚氧化烯烷苯醚之構造者為特佳。
作為使用之濃度,只要有充分的效果則不特別限制之,考慮到發揮充分效果與保存時之安定性等,以0.01~5wt%為佳,以0.05~2wt%為更佳。
又,在使用鹼性溶液之洗淨或蝕刻步驟中,Ni吸附於基板表面之量越少越好,但習知的鹼性水溶液於蝕刻步驟中無法將Ni吸附於矽晶圓表面之量抑制在20×1010
atoms/cm2
以下。
於此,在一般半導體製造步驟中,用本發明之鹼性水溶液組成物洗淨或蝕刻後之矽晶圓表面的Ni濃度,以20×1010
atoms/cm2
以下為佳,以15×1010
atoms/cm2
以下為較佳,以於P+
型低電阻晶圓中成為10×1010
atoms/cm2
以下為更佳。
因此,本發明之鹼性水溶液組成物,能夠充分發揮於半導體製造步驟等中所期待之防止Ni吸附於矽晶圓等基板表面之效果。
以下藉由實施例及比較例更詳細地說明本發明,惟本發明並不僅限於該等實施例,於不脫離本發明技術思想範圍內,可以做各種變更。
(高濃度氫氧化鈉蝕刻液)
將清潔之矽晶圓(P+
型,電阻率0.01~0.02Ω.cm)25℃下浸泡在0.5重量%濃度之稀氫氟酸中1分鐘後,用水洗1分鐘,去除自然氧化膜。將此矽晶圓於80℃下浸泡在用水作為溶劑而以表1所示之組成製備而成的處理液中10分鐘,進行蝕刻之後,進行5分鐘水洗,然後乾燥。用全反射X射線螢光光譜儀測量此矽晶圓表面的Fe及Ni濃度。測量結果表示於表1。
從表1的結果可清楚了解,在使用氫氧化鈉為48重量%之強鹼性蝕刻液來蝕刻的情形中,於不添加螯合劑的情況下,可觀察到Fe吸附為1015
atoms/cm2
程度、Ni吸附為1014
atoms/cm2
程度,而於本發明實施例1中,不管與其他任一比較例比較,矽晶圓表面的Fe及Ni濃度都非常低,證實了本發明能夠極為有效果地防止金屬吸附。
(氫氧化四甲基銨洗淨液)
分別將濃度調整成10ppb之Fe及Ni原子吸光用標準液塗佈於清潔之矽晶圓上,放置1分鐘,用Fe及Ni污染之。將此矽晶圓於25℃下浸泡在用水作為溶劑而以表2
所示之組成製備而成的處理液中3分鐘,將其洗淨後,進行3分鐘超純水流水清洗。清洗後將矽晶圓乾燥,用全反射X射線螢光光譜儀測量此矽晶圓處理前後之Fe及Ni的表面濃度,評量其對Fe及Ni之洗淨能力。測量結果表示於表2。
此外,洗淨前的矽晶圓表面的污染程度,Fe及Ni皆為1013
atoms/cm2
。
從表2的結果可清楚了解,於使用含有有機鹼成分TMAH之強鹼洗淨液來洗淨的情形中,不管於本發明任一實施例中,比起其他比較例,矽晶圓表面的Fe及Ni濃度都非常低,證實了本發明能夠極為有效果地防止金屬吸附及洗淨金屬。
Claims (11)
- 一種水溶液組成物,係用於矽晶圓或是玻璃基板洗淨或蝕刻之鹼性水溶液組成物,防止金屬吸附於前述矽晶圓或是玻璃基板上,其含有結構式(1)表示之螯合劑以及鹼性成分;
- 如申請專利範圍第1項所述之水溶液組成物,其中該 螯合劑為N,N’-雙(亞柳基)-1,2-乙二胺、N,N’-雙(亞柳基)-1,2-丙二胺或N,N’-雙(亞柳基)-1,3-丙二胺。
- 如申請專利範圍第1項所述之水溶液組成物,其中鹼性成分為氫氧化四甲基銨。
- 如申請專利範圍第1項所述之水溶液組成物,其中鹼性成分為氫氧化鈉及/或氫氧化鉀。
- 如申請專利範圍第1項所述之水溶液組成物,其中更含有其他螯合劑。
- 如申請專利範圍第1項所述之水溶液組成物,其係用於洗淨液,其中鹼性成分的濃度為0.01~1.0wt%、螯合劑的濃度為0.0005~1.0wt%。
- 如申請專利範圍第6項所述之水溶液組成物,其中更含有防蝕劑。
- 如申請專利範圍第6項所述之水溶液組成物,其中更含有界面活性劑。
- 如申請專利範圍第1項所述之水溶液組成物,其係用於蝕刻液,其中鹼性成分的濃度為1.0~50wt%、螯合劑的濃度為0.001~5.0wt%。
- 如申請專利範圍第1項所述之水溶液組成物,其中,於洗淨或蝕刻後的矽晶圓表面的Ni濃度變成20×1010 atoms/cm2 以下。
- 一種矽晶圓或是玻璃基板洗淨或蝕刻的方法,係用申請專利範圍第1項所述之水溶液組成物,將矽晶圓或是玻 璃基板洗淨或蝕刻,使該矽晶圓或是玻璃基板表面的Ni濃度在20×1010 atoms/cm2 以下。
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DE112010003900T5 (de) * | 2009-10-02 | 2012-08-30 | Mitsubishi Gas Chemical Company, Inc. | Lösung zum Ätzen von Silizium und Ätz-Verfahren |
US8883701B2 (en) * | 2010-07-09 | 2014-11-11 | Air Products And Chemicals, Inc. | Method for wafer dicing and composition useful thereof |
US9873833B2 (en) | 2014-12-29 | 2018-01-23 | Versum Materials Us, Llc | Etchant solutions and method of use thereof |
CN105154268A (zh) * | 2015-08-29 | 2015-12-16 | 江西赛维Ldk太阳能高科技有限公司 | 一种可减少硅片表面损伤层厚度的清洗液及清洗方法 |
JP6674628B2 (ja) * | 2016-04-26 | 2020-04-01 | 信越化学工業株式会社 | 洗浄剤組成物及び薄型基板の製造方法 |
JP6887722B2 (ja) * | 2016-10-25 | 2021-06-16 | 株式会社ディスコ | ウェーハの加工方法及び切削装置 |
WO2019208614A1 (ja) * | 2018-04-26 | 2019-10-31 | 三菱瓦斯化学株式会社 | 樹脂組成物、積層体、樹脂組成物層付き半導体ウェハ、樹脂組成物層付き半導体搭載用基板、及び半導体装置 |
KR102678071B1 (ko) * | 2019-01-08 | 2024-06-24 | 동우 화인켐 주식회사 | 실리콘 막 식각액 조성물 및 이를 사용한 패턴 형성 방법 |
KR20210143166A (ko) * | 2019-03-26 | 2021-11-26 | 가부시키가이샤 후지미인코퍼레이티드 | 표면 처리 조성물, 그 제조 방법, 표면 처리 방법 및 반도체 기판의 제조 방법 |
TW202106647A (zh) | 2019-05-15 | 2021-02-16 | 美商康寧公司 | 在高溫下用高濃度鹼金屬氫氧化物減少紋理化玻璃、玻璃陶瓷以及陶瓷製品之厚度的方法 |
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DE102020133278A1 (de) * | 2020-12-14 | 2022-06-15 | Schott Ag | Verfahren zur Herstellung strukturierter Glasartikel durch alkalische Ätzung |
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KR101482154B1 (ko) | 2015-01-13 |
JP5142592B2 (ja) | 2013-02-13 |
JP2008305900A (ja) | 2008-12-18 |
CN101319172B (zh) | 2012-06-27 |
US8123976B2 (en) | 2012-02-28 |
US20090001315A1 (en) | 2009-01-01 |
KR20080107306A (ko) | 2008-12-10 |
TW200907048A (en) | 2009-02-16 |
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