JP7273170B2 - コバルト又は銅合金の電着、及びマイクロエレクトロニクスにおける使用 - Google Patents
コバルト又は銅合金の電着、及びマイクロエレクトロニクスにおける使用 Download PDFInfo
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- JP7273170B2 JP7273170B2 JP2021546683A JP2021546683A JP7273170B2 JP 7273170 B2 JP7273170 B2 JP 7273170B2 JP 2021546683 A JP2021546683 A JP 2021546683A JP 2021546683 A JP2021546683 A JP 2021546683A JP 7273170 B2 JP7273170 B2 JP 7273170B2
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- cobalt
- metal
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- ions
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- 239000010941 cobalt Substances 0.000 title claims description 115
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims description 112
- 238000004070 electrodeposition Methods 0.000 title description 20
- 229910000531 Co alloy Inorganic materials 0.000 title description 7
- 229910000881 Cu alloy Inorganic materials 0.000 title description 3
- 238000004377 microelectronic Methods 0.000 title 1
- 229910017052 cobalt Inorganic materials 0.000 claims description 108
- 229910052751 metal Inorganic materials 0.000 claims description 70
- 239000002184 metal Substances 0.000 claims description 70
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 63
- 239000010949 copper Substances 0.000 claims description 63
- 229910052802 copper Inorganic materials 0.000 claims description 63
- 238000000034 method Methods 0.000 claims description 57
- 230000008569 process Effects 0.000 claims description 44
- 150000002500 ions Chemical class 0.000 claims description 42
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 37
- 239000003792 electrolyte Substances 0.000 claims description 37
- 239000011701 zinc Substances 0.000 claims description 36
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 35
- 229910052725 zinc Inorganic materials 0.000 claims description 35
- 239000011572 manganese Substances 0.000 claims description 34
- 229910052748 manganese Inorganic materials 0.000 claims description 34
- 239000006259 organic additive Substances 0.000 claims description 32
- 229910045601 alloy Inorganic materials 0.000 claims description 30
- 239000000956 alloy Substances 0.000 claims description 30
- 238000011049 filling Methods 0.000 claims description 22
- 238000000137 annealing Methods 0.000 claims description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 16
- 229910021645 metal ion Inorganic materials 0.000 claims description 14
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 239000008151 electrolyte solution Substances 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 9
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 8
- 239000011975 tartaric acid Substances 0.000 claims description 8
- 235000002906 tartaric acid Nutrition 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 7
- 150000007524 organic acids Chemical class 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 235000012239 silicon dioxide Nutrition 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 150000007522 mineralic acids Chemical class 0.000 claims description 6
- 239000003989 dielectric material Substances 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 5
- QBYIENPQHBMVBV-HFEGYEGKSA-N (2R)-2-hydroxy-2-phenylacetic acid Chemical compound O[C@@H](C(O)=O)c1ccccc1.O[C@@H](C(O)=O)c1ccccc1 QBYIENPQHBMVBV-HFEGYEGKSA-N 0.000 claims description 4
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 4
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 4
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 4
- IWYDHOAUDWTVEP-UHFFFAOYSA-N R-2-phenyl-2-hydroxyacetic acid Natural products OC(=O)C(O)C1=CC=CC=C1 IWYDHOAUDWTVEP-UHFFFAOYSA-N 0.000 claims description 4
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000001630 malic acid Substances 0.000 claims description 4
- 235000011090 malic acid Nutrition 0.000 claims description 4
- 229960002510 mandelic acid Drugs 0.000 claims description 4
- 229910052715 tantalum Inorganic materials 0.000 claims description 4
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- AFENDNXGAFYKQO-VKHMYHEASA-N (S)-2-hydroxybutyric acid Chemical compound CC[C@H](O)C(O)=O AFENDNXGAFYKQO-VKHMYHEASA-N 0.000 claims description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- 239000004310 lactic acid Substances 0.000 claims description 2
- 235000014655 lactic acid Nutrition 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 229960001939 zinc chloride Drugs 0.000 claims 1
- 239000000758 substrate Substances 0.000 description 30
- 238000000151 deposition Methods 0.000 description 23
- 239000000463 material Substances 0.000 description 19
- 230000008021 deposition Effects 0.000 description 17
- 239000000654 additive Substances 0.000 description 16
- 230000010287 polarization Effects 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- 229910001429 cobalt ion Inorganic materials 0.000 description 8
- 239000003112 inhibitor Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 7
- 230000000996 additive effect Effects 0.000 description 7
- 239000012535 impurity Substances 0.000 description 7
- -1 sulphates Chemical class 0.000 description 7
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 6
- 229910000914 Mn alloy Inorganic materials 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 229910001297 Zn alloy Inorganic materials 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 6
- 229910001431 copper ion Inorganic materials 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 5
- 238000011109 contamination Methods 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
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- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
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- 230000015572 biosynthetic process Effects 0.000 description 4
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- PXQPEWDEAKTCGB-UHFFFAOYSA-N orotic acid Chemical compound OC(=O)C1=CC(=O)NC(=O)N1 PXQPEWDEAKTCGB-UHFFFAOYSA-N 0.000 description 4
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- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 4
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- 239000011800 void material Substances 0.000 description 4
- OBDVFOBWBHMJDG-UHFFFAOYSA-N 3-mercapto-1-propanesulfonic acid Chemical compound OS(=O)(=O)CCCS OBDVFOBWBHMJDG-UHFFFAOYSA-N 0.000 description 3
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- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical compound [Mn].[Co] MZZUATUOLXMCEY-UHFFFAOYSA-N 0.000 description 3
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- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N propylene glycol Substances CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical class C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/18—Electroplating using modulated, pulsed or reversing current
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/58—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of copper
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
- C25D5/50—After-treatment of electroplated surfaces by heat-treatment
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/12—Semiconductors
- C25D7/123—Semiconductors first coated with a seed layer or a conductive layer
-
- 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
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
- H01L21/288—Deposition of conductive or insulating materials for electrodes conducting electric current from a liquid, e.g. electrolytic deposition
- H01L21/2885—Deposition of conductive or insulating materials for electrodes conducting electric current from a liquid, e.g. electrolytic deposition using an external electrical current, i.e. electro-deposition
-
- 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
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
- H01L21/76841—Barrier, adhesion or liner layers
- H01L21/76867—Barrier, adhesion or liner layers characterized by methods of formation other than PVD, CVD or deposition from a liquids
-
- 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
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
- H01L21/76877—Filling of holes, grooves or trenches, e.g. vias, with conductive material
-
- 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
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
- H01L21/76877—Filling of holes, grooves or trenches, e.g. vias, with conductive material
- H01L21/76883—Post-treatment or after-treatment of the conductive material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/52—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames
- H01L23/522—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body
- H01L23/532—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body characterised by the materials
- H01L23/53204—Conductive materials
- H01L23/53209—Conductive materials based on metals, e.g. alloys, metal silicides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/52—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames
- H01L23/522—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body
- H01L23/532—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body characterised by the materials
- H01L23/53204—Conductive materials
- H01L23/53209—Conductive materials based on metals, e.g. alloys, metal silicides
- H01L23/53228—Conductive materials based on metals, e.g. alloys, metal silicides the principal metal being copper
- H01L23/53238—Additional layers associated with copper layers, e.g. adhesion, barrier, cladding layers
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- Power Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
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- Microelectronics & Electronic Packaging (AREA)
- Computer Hardware Design (AREA)
- Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
Description
・質量濃度が1g/L~5g/LのコバルトIIイオン又は銅IIイオン、
・質量濃度が1g/L~10g/Lの塩化物イオン、
・マンガンIIイオン及び亜鉛IIイオンから選択される金属イオンであって、コバルトIIイオン又は銅IIイオンの質量濃度と金属イオンの質量濃度との比が1/10~25/1となるような質量濃度の金属イオン、
・上記電解液のpHを1.8~4.0とするのに十分な量の有機酸又は無機酸、及び
・ポリマーではない1つのみ又は多くとも2つの有機添加物であって、上記1つの有機添加物、上記2つの有機添加物のうちの1つ、又は上記2つの有機添加物は、組成物中に上記有機酸が存在する場合は上記有機酸であってもよく、上記1つの有機添加物の濃度又は上記2つの有機添加物の濃度の合計が、5mg/L~200mg/Lである有機添加物
を含む水溶液であることを特徴とする電解液に関する。
「電解液」とは、電着プロセスにおいて使用される金属コーティングの前駆体を含む液体をいう。
・質量濃度が1g/L~5g/LのコバルトIIイオン又は銅IIイオン、
・質量濃度が1g/L~10g/Lの塩化物イオン、
・マンガンIIイオン及び亜鉛IIイオンから選択される金属イオンであって、コバルトIIイオン又は銅IIイオンの質量濃度と金属イオンの質量濃度との比が1/10~10/1となるような質量濃度の金属イオン、
・pHを1.8~4.0とするのに十分な量の有機酸又は無機酸、及び
・ポリマーではない1つのみ又は多くとも2つの有機添加物であって、上記2つの有機添加物のうちの1つは上記酸であってもよく、当該酸が有機酸である場合、上記1つの添加物の濃度又は上記2つの添加物の濃度の合計が、5mg/L~200mg/Lである有機添加物
を含む水溶液であることを特徴とする電解液に関する。
・パターンの底部におけるコバルト又は銅の成長の促進剤を含まない。
・電解液は、電着時に空洞の開口部における基板の平坦部に堆積するコバルト又は銅に特異的に吸着することにより、当該部位上のコバルト又は銅の成長を遅らせることができる有機抑制分子を含まない。
・ボトムアップ充填機構を生じさせる添加物の組み合わせ、特に抑制剤と促進剤との組み合わせ、又は抑制剤と、促進剤と、平坦化剤との組み合わせを含まない。
・ポリマーを含まない(ポリマーとは、少なくとも4つの繰り返し単位を有する分子を意味する)。
・含硫化合物を含まない。
・基板分極時間の間、電解液のpHを1.8又は2.0より高く、3.5より低い、好ましくは2.5より低い値に維持できるような、溝内の表面上での局所緩衝能。
・開口部の平均直径が小さい構造又は平均幅が小さい構造に添加物が拡散することができるような低分子量。
・分極の開始前に電解液中に存在する添加物のほぼ全量が構造の空洞内に拡散し、添加物が局所緩衝能を有するような、非常に低い電解液中の濃度。
・質量濃度が1g/L~5g/LのコバルトIIイオン、
・質量濃度が1g/L~5g/Lの塩化物イオン、
・コバルトIIイオンの質量濃度と亜鉛IIイオンの質量濃度との比が15/1~20/1となるような質量濃度の亜鉛IIイオン、
・pHを2.0~2.4とするのに十分な量の無機酸、及び
・濃度が10mg/L~20mg/Lの1つのみの有機添加物
を含む水溶液である。
・上記空洞の導電性表面に、上記記載に従った電解液を接触させる工程、
・コバルト、銅及びこれらの混合物から選択される第1の金属と、マンガン、亜鉛及びこれらの混合物から選択される第2の金属との合金を堆積させて上記空洞のコンフォーマルかつ完全な充填を実施するのに十分な時間、上記導電性表面を分極する工程、及び
・上記分極工程の終了時に得られた合金の堆積物をアニーリングする工程であって、上記アニーリングは、上記金属を移動させることで、上記金属を主に含み、厚さが0.5nm~2nmの第1の層と、本質的にコバルト又は銅を含む第2の層とを形成する温度で行われる工程
を含むプロセスに関する。
・シリコン基板に構造体をエッチングする工程
・構造体のシリコン面に酸化ケイ素の層を形成し、酸化ケイ素面を形成する工程
・上記酸化ケイ素の層の上に金属の層を堆積させて、空洞に導電性表面を付与する工程
基板
この例で使用される基板は、4×4cmのシリコン試験片からなる。このシリコンは、厚さ3nmのタンタル層に接した酸化ケイ素で覆われており、タンタル層自体は厚さ3nmのコバルト層で覆われ、CVDで堆積されている。測定された基板の抵抗率は約168Ω/□である。
この溶液中のCo2+濃度は2.35g/Lであり、CoCl2(H2O)6から得られる。Zn2+濃度は0.136g/Lであり、ZnCl2から得られる。酒石酸は15mg/Lで含まれる。
この溶液に塩酸を加えてpH=2.2に調整する。
本実施例で使用した電解堆積装置は、セル及び回転電極の2つの部分から構成されていた。セルは、電解液を収容するもので、系の流体力学を制御する流体再循環システムを備えていた。回転電極は、使用する試験片の大きさ(4cm×4cm)に適した試料ホルダを備えていた。電解堆積セルは下記2つの電極から構成されていた。
・コバルトアノード
・カソードを構成する、上記層で被覆されたシリコン試験片
リファレンスはアノードに接続される。
コネクタにより電極の電気的接触を可能にし、20V又は2Aまで供給するポテンショスタットに電線で接続した。
準備手順
基板は、一般に、ウエハが古くなっているか、又は保管状態が悪いために、自然酸化コバルト層が大きすぎる場合にのみ、特別な処理を必要とする。保管は通常、窒素下で行われる。この場合、水素(純粋な水素、又は窒素中に4%の水素を含む混合ガスのいずれか)を含むプラズマを発生させる必要がある。
プロセスは以下のように実行される。50mA(又は11mA/cm2)~120mA(又は26mA/cm2)、例えば100mA(又は22.1mA/cm2)の電流範囲で、連続ガルバニックモードでカソード分極を行った。この工程は、60rpmの回転で1時間行った。電解液は、電圧を印加する前に、基板に5秒間接触させる。合金の堆積速度は3.3nm/sである。別の実施形態では、80mA(又は17.6mA/cm2)~160mA(又は35.2mA/cm2)、例えば130mA(又は28.6mA/cm2)の電流範囲で、ガルバノパルスモードでカソード分極を行い、パルス持続時間はカソード分極時には5ms~1000ms、2つのカソードパルス間のゼロ分極時には5ms~1000msであった。
400℃、水素含有雰囲気下(窒素中4%水素)で30分間アニーリングを行い、SiO2とコバルトとの界面へ亜鉛を移動させた。
走査電子顕微鏡法によるプロファイル解析の結果、合金の厚さはおよそ200nmであった。この厚さは、アニーリング後にわずかに減少し、190nmとなった。アニーリング前のXPS分析によれば、合金中には2原子%程度の亜鉛が存在していた。しかしながら、アニーリング後に同様の形式で分析を行うと、SiO2-コバルト界面及び最も外側の表面の両方に向かって亜鉛が移動していた。一方、酸素、炭素及び窒素による全汚染率が600原子ppmを超えることはなかった。
Claims (7)
- コバルトである第1の金属と、マンガン、亜鉛及びこれらの混合物から選択される第2の金属との合金を電着するための電解液であって、
質量濃度が1g/L~5g/LのコバルトIIイオン、
質量濃度が1g/L~10g/Lの塩化物イオン、
マンガンIIイオン及び亜鉛IIイオンから選択される金属イオンであって、コバルトIIイオンの質量濃度と金属イオンの質量濃度との比が1/10~25/1となるような質量濃度の金属イオン(前記コバルトIIイオン、前記塩化物イオン、前記マンガンIIイオン、及び、前記亜鉛IIイオンにおける各質量濃度は、塩化コバルト、塩化コバルト六水和物、塩化マンガン、塩化亜鉛を水に溶解することによって得られるものである)、
上記電解液のpHを1.8~4.0に維持する、十分な量の有機酸又は無機強酸、及び、
ポリマーではない2つ以下の有機添加物であって、上記2つ以下の有機添加物の少なくとも1つは、水溶液中に上記有機酸として存在し、上記有機酸は、クエン酸、酒石酸、グリコール酸、乳酸、リンゴ酸、マンデル酸、シュウ酸、及び、2-ヒドロキシ酪酸から選択されるα-ヒドロキシカルボン酸であり、上記2つ以下の有機添加物の濃度が、5mg/L~200mg/Lである有機添加物
を含む水溶液であることを特徴とする電解液。 - 上記無機強酸が塩酸であることを特徴とする請求項1に記載の電解液。
- 上記pHが2.0~3.5であることを特徴とする請求項1又は2に記載の電解液。
- 上記有機添加物が単一の有機添加物を含み、該単一の有機添加物は酒石酸であることを特徴とする請求項1に記載の電解液。
- 空洞を充填するための電気化学プロセスであって、
上記空洞の開口部における平均幅又は平均直径は15nm~100nmであり、深さは50nm~250nmであり、
上記空洞の導電性表面に、請求項1~4のいずれか1項に記載の電解液を接触させる工程、
コバルトである第1の金属と、マンガン、亜鉛及びこれらの混合物から選択される第2の金属との合金を堆積させて上記空洞のコンフォーマルかつ完全な充填を実施するのに十分な時間、上記導電性表面を分極する工程、及び、
上記分極工程の終了時に得られた合金の堆積物をアニーリングする工程であって、上記アニーリングは、上記第2の金属を移動させることで、上記第2の金属を主に含み、かつ上記導電性表面と接触している厚さが0.5nm~2nmの第1の層と、本質的にコバルトを含み、かつ上記第1の層の表面を被覆する第2の層であって、上記導電性表面と接触していない第2の層とを形成できる温度で行われる工程
を含む電気化学プロセス。 - 上記導電性表面が、金属シード層の第1の表面であり、上記金属シード層が、上記第2の金属とは異なる第3の金属からなり、上記金属シード層の厚さが1nm~10nmであり、上記金属シード層が、二酸化ケイ素を含む誘電体材料と接触している第2の表面を有することを特徴とする請求項5に記載のプロセス。
- 上記第3の金属が、コバルト、銅、タングステン、チタン、タンタル、ルテニウム、ニッケル、及び、これらの混合物からなる群から選択されることを特徴とする請求項6に記載のプロセス。
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FR1901264A FR3092589A1 (fr) | 2019-02-08 | 2019-02-08 | Electrodéposition d’un alliage de cobalt et utilisation en microélectronique |
FR2000297A FR3092590A1 (fr) | 2019-02-08 | 2020-01-14 | Electrodéposition d’un alliage de cobalt ou de cuivre, et utilisation en microélectronique |
FR2000297 | 2020-01-14 | ||
PCT/EP2020/053018 WO2020161256A1 (en) | 2019-02-08 | 2020-02-06 | Electrodeposition of a cobalt or copper alloy, and use in microelectronics |
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US20030064243A1 (en) | 2000-12-22 | 2003-04-03 | Myung-Su Kim | Zn-co-w alloy electroplated steel sheet with excellent corrosion resistance and welding property, and its electrolyte for it |
JP2004068138A (ja) | 2002-08-09 | 2004-03-04 | Nippon Parkerizing Co Ltd | 黒色合金めっき液 |
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US20120141667A1 (en) * | 2010-07-16 | 2012-06-07 | Applied Materials, Inc. | Methods for forming barrier/seed layers for copper interconnect structures |
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US20030064243A1 (en) | 2000-12-22 | 2003-04-03 | Myung-Su Kim | Zn-co-w alloy electroplated steel sheet with excellent corrosion resistance and welding property, and its electrolyte for it |
JP2004068138A (ja) | 2002-08-09 | 2004-03-04 | Nippon Parkerizing Co Ltd | 黒色合金めっき液 |
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