JP2008510076A - 表面活性化剤を用いた銅の原子層蒸着 - Google Patents
表面活性化剤を用いた銅の原子層蒸着 Download PDFInfo
- Publication number
- JP2008510076A JP2008510076A JP2007528021A JP2007528021A JP2008510076A JP 2008510076 A JP2008510076 A JP 2008510076A JP 2007528021 A JP2007528021 A JP 2007528021A JP 2007528021 A JP2007528021 A JP 2007528021A JP 2008510076 A JP2008510076 A JP 2008510076A
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- JP
- Japan
- Prior art keywords
- group
- copper
- substrate
- alkyl
- independently selected
- 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.)
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 36
- 239000010949 copper Substances 0.000 title claims abstract description 36
- 239000012190 activator Substances 0.000 title claims description 16
- 238000000231 atomic layer deposition Methods 0.000 title abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 51
- 239000000758 substrate Substances 0.000 claims abstract description 50
- 239000012691 Cu precursor Substances 0.000 claims description 28
- 239000003638 chemical reducing agent Substances 0.000 claims description 25
- 229910052739 hydrogen Inorganic materials 0.000 claims description 22
- 150000004699 copper complex Chemical class 0.000 claims description 21
- 238000000151 deposition Methods 0.000 claims description 20
- 239000003446 ligand Substances 0.000 claims description 19
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- -1 4-pyridinyl Chemical group 0.000 claims description 13
- 230000003213 activating effect Effects 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 12
- FEJUGLKDZJDVFY-UHFFFAOYSA-N 9-borabicyclo(3.3.1)nonane Chemical group C1CCC2CCCC1B2 FEJUGLKDZJDVFY-UHFFFAOYSA-N 0.000 claims description 10
- HBEDSQVIWPRPAY-UHFFFAOYSA-N 2,3-dihydrobenzofuran Chemical compound C1=CC=C2OCCC2=C1 HBEDSQVIWPRPAY-UHFFFAOYSA-N 0.000 claims description 8
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 8
- 150000001879 copper Chemical class 0.000 claims description 8
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 7
- UCXUKTLCVSGCNR-UHFFFAOYSA-N diethylsilane Chemical compound CC[SiH2]CC UCXUKTLCVSGCNR-UHFFFAOYSA-N 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 238000010926 purge Methods 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 6
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 6
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 239000011737 fluorine Substances 0.000 claims description 6
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 claims description 6
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 230000004888 barrier function Effects 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 5
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims description 4
- 229910000085 borane Inorganic materials 0.000 claims description 4
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910000078 germane Chemical group 0.000 claims description 4
- 150000002825 nitriles Chemical class 0.000 claims description 4
- 150000003003 phosphines Chemical class 0.000 claims description 4
- DNXIASIHZYFFRO-UHFFFAOYSA-N pyrazoline Chemical compound C1CN=NC1 DNXIASIHZYFFRO-UHFFFAOYSA-N 0.000 claims description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 229910000077 silane Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 125000006724 (C1-C5) alkyl ester group Chemical group 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- CFJRGWXELQQLSA-UHFFFAOYSA-N azanylidyneniobium Chemical compound [Nb]#N CFJRGWXELQQLSA-UHFFFAOYSA-N 0.000 claims description 2
- AZOFWQDMTKZNMJ-UHFFFAOYSA-N copper 1-(dimethylamino)propan-1-olate Chemical compound [Cu++].CCC([O-])N(C)C.CCC([O-])N(C)C AZOFWQDMTKZNMJ-UHFFFAOYSA-N 0.000 claims description 2
- AYNKDSOCVPQIEG-UHFFFAOYSA-N copper 1-aminoethanolate Chemical compound NC([O-])C.[Cu+2].NC([O-])C AYNKDSOCVPQIEG-UHFFFAOYSA-N 0.000 claims description 2
- UTQPYFQVJZORSD-UHFFFAOYSA-N copper bis(trimethylsilyl)azanide Chemical compound [Cu+2].C[Si](C)(C)[N-][Si](C)(C)C.C[Si](C)(C)[N-][Si](C)(C)C UTQPYFQVJZORSD-UHFFFAOYSA-N 0.000 claims description 2
- UBHZUDXTHNMNLD-UHFFFAOYSA-N dimethylsilane Chemical compound C[SiH2]C UBHZUDXTHNMNLD-UHFFFAOYSA-N 0.000 claims description 2
- KCWYOFZQRFCIIE-UHFFFAOYSA-N ethylsilane Chemical compound CC[SiH3] KCWYOFZQRFCIIE-UHFFFAOYSA-N 0.000 claims description 2
- 150000002466 imines Chemical class 0.000 claims description 2
- 230000005012 migration Effects 0.000 claims description 2
- 238000013508 migration Methods 0.000 claims description 2
- UUEVFMOUBSLVJW-UHFFFAOYSA-N oxo-[[1-[2-[2-[2-[4-(oxoazaniumylmethylidene)pyridin-1-yl]ethoxy]ethoxy]ethyl]pyridin-4-ylidene]methyl]azanium;dibromide Chemical compound [Br-].[Br-].C1=CC(=C[NH+]=O)C=CN1CCOCCOCCN1C=CC(=C[NH+]=O)C=C1 UUEVFMOUBSLVJW-UHFFFAOYSA-N 0.000 claims description 2
- PARWUHTVGZSQPD-UHFFFAOYSA-N phenylsilane Chemical compound [SiH3]C1=CC=CC=C1 PARWUHTVGZSQPD-UHFFFAOYSA-N 0.000 claims description 2
- 150000004756 silanes Chemical class 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- SNOOUWRIMMFWNE-UHFFFAOYSA-M sodium;6-[(3,4,5-trimethoxybenzoyl)amino]hexanoate Chemical compound [Na+].COC1=CC(C(=O)NCCCCCC([O-])=O)=CC(OC)=C1OC SNOOUWRIMMFWNE-UHFFFAOYSA-M 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical group [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- NOIXNOMHHWGUTG-UHFFFAOYSA-N 2-[[4-[4-pyridin-4-yl-1-(2,2,2-trifluoroethyl)pyrazol-3-yl]phenoxy]methyl]quinoline Chemical compound C=1C=C(OCC=2N=C3C=CC=CC3=CC=2)C=CC=1C1=NN(CC(F)(F)F)C=C1C1=CC=NC=C1 NOIXNOMHHWGUTG-UHFFFAOYSA-N 0.000 claims 1
- SDTMFDGELKWGFT-UHFFFAOYSA-N 2-methylpropan-2-olate Chemical compound CC(C)(C)[O-] SDTMFDGELKWGFT-UHFFFAOYSA-N 0.000 claims 1
- 239000007787 solid Substances 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 19
- 230000008021 deposition Effects 0.000 description 16
- 239000003153 chemical reaction reagent Substances 0.000 description 11
- 239000002243 precursor Substances 0.000 description 9
- 239000010410 layer Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000006722 reduction reaction Methods 0.000 description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 238000007740 vapor deposition Methods 0.000 description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- 239000002356 single layer Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000005979 thermal decomposition reaction Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 150000004696 coordination complex Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- GUHKMHMGKKRFDT-UHFFFAOYSA-N 1785-64-4 Chemical compound C1CC(=C(F)C=2F)C(F)=C(F)C=2CCC2=C(F)C(F)=C1C(F)=C2F GUHKMHMGKKRFDT-UHFFFAOYSA-N 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000005588 protonation Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- HUVAAOZUPLEYBH-UHFFFAOYSA-N 3,4,5-trimethyl-1h-pyrazole Chemical compound CC1=NNC(C)=C1C HUVAAOZUPLEYBH-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000004964 aerogel Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- WILFNLHOTDCRAO-UHFFFAOYSA-N copper(1+);2-methylpropan-2-olate Chemical compound [Cu+].CC(C)(C)[O-] WILFNLHOTDCRAO-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003217 pyrazoles Chemical class 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Classifications
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- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
- C23C16/45534—Use of auxiliary reactants other than used for contributing to the composition of the main film, e.g. catalysts, activators or scavengers
-
- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/02—Pretreatment of the material to be coated
-
- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
-
- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
- C23C16/18—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metallo-organic compounds
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- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/448—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials
-
- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45553—Atomic layer deposition [ALD] characterized by the use of precursors specially adapted for ALD
-
- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
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- 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
- H01L21/285—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation
- H01L21/28506—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers
- H01L21/28512—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table
- H01L21/28556—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table by chemical means, e.g. CVD, LPCVD, PECVD, laser CVD
- H01L21/28562—Selective deposition
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- 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
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Abstract
Description
a.基材を表面活性化剤に曝露して、基材上に表面活性化基の蒸着物(a deposit of a surface−activating group)を形成する工程と、
b.基材上の表面活性化基の蒸着物を銅前駆体に曝露して、基材上に銅錯体の蒸着物を形成する工程と、
c.蒸着された銅錯体と還元剤とを反応させて、基材上に銅金属の蒸着物を形成する工程と
を含んでなる、銅膜を表面上に蒸着する方法である。
R1およびR4は独立してH、C1〜C5アルキル、およびジメチルアミノよりなる群から選択され、
R2およびR3は独立してH、C1〜C5アルキル、フェニル、ベンジル、および4−ピリジニルよりなる群から選択されるが、ただし、このリガンドのR1〜R4における炭素の総数は4〜12である]
R5およびR8はジメチルアミノであり、そして
R6およびR7は独立してH、C1〜C5アルキル、フェニル、ベンジル、および4−ピリジニルよりなる群から選択されるが、ただし、このリガンドのR5〜R8における炭素の総数は4〜14である、または
R5およびR8は独立してH、C1〜C5アルキル、およびジメチルアミノよりなる群から選択され、そして
R6およびR7はH、C1〜C5アルキル、フェニル、ベンジル、および4−ピリジニルよりなる群から選択されるが、ただし、R6またはR7の一方は4−ピリジニルであり、かつ
このリガンドのR5〜R8における炭素の総数は4〜14である]
R1、R2およびR3は独立して水素、メチル、エチル、プロピル、イソプロピル、イソブチル、およびネオペンチルよりなる群から選択され、R4は−(CH2)n−であり、式中、nは3、4、または5である]
LはC2〜C15オレフィン、C2〜C15アルキン、ニトリル、芳香族複素環、およびホスフィンの群から選択され、
R1およびR4は独立して水素、メチル、エチル、プロピル、イソプロピル、イソブチル、およびネオペンチルよりなる群から選択され、
R2、R3およびR5は独立して水素、フッ素、トリフルオロメチル、フェニルおよびC1〜C10アルキル基よりなる群から選択される]
ならびに
LはC2〜C15オレフィン、C2〜C15アルキン、ニトリル、芳香族複素環、およびホスフィンの群から選択され、
R1およびR4は独立して水素、メチル、エチル、プロピル、イソプロピル、イソブチル、ネオペンチルおよびC3〜C5アルキレンよりなる群から選択され、
R2、R3およびR5は独立して水素、フッ素、トリフルオロメチル、フェニル、C1〜C10アルキルおよびC3〜C5アルキレンよりなる群から選択されるが、ただし(R1、R2)および(R3、R4)の少なくとも一方は一緒になって−(CR6R7)n−、ここで、R6およびR7は独立して水素、フッ素、トリフルオロメチル、C1〜C5アルキル、C1〜C5アルキルエステルよりなる群から選択され、nは3、4または5である、である]
銅膜の蒸着
文献の方法(国際特許出願第PCT/US2004/011734号明細書、2004年4月16日)に従って銅前駆体(ビニルトリメチルシリル)(N,N’−ジエチル−2,4−ペンタンジケトイミナト)銅(I)を調製した。Ti/SiO2/Siウェハ上への金の蒸着により金膜を調製した。ウェハを0.6cm×0.6cmの切片に切り取った。金層は750Å厚であった。使用前に、切片を10−9torrでスパッタエッチングして清浄な金表面とし、および真空移送容器中に、連続的なボイルオフ窒素パージで真空雰囲気ドライボックスに移した(ウェハは、周囲雰囲気に曝露されていない)。ウェハを蒸着反応の前に2時間250℃で加熱した。
Claims (19)
- a.基材を表面活性化剤に曝露して、基材上に表面活性化基の蒸着物を形成する工程と、
b.基材上の表面活性化基の蒸着物を銅前駆体に曝露して、基材上に銅錯体の蒸着物を形成する工程と、
c.蒸着した銅錯体を還元剤と反応させて、基材上に銅金属の蒸着物を形成する工程と
を含んでなる、表面上に銅膜を蒸着する方法。 - 銅前駆体が、ビス(アミノエタノレート)銅(II)、銅(I)ジアルキルアミド、ビス(ジメチルアミノプロパノレート)銅(II)、(ビス(トリメチルシリル)アミド)−銅(I)、および銅(I)t−ブトキシドよりなる群から選択される請求項1に記載の方法。
- 銅前駆体が、構造(II)
[式中、
R5およびR8はジメチルアミノであり、そして
R6およびR7は独立してH、C1〜C5アルキル、フェニル、ベンジル、および4−ピリジニルよりなる群から選択されるが、ただし、このリガンドのR5〜R8における炭素の総数は4〜14である、または
R5およびR8は独立してH、C1〜C5アルキル、およびジメチルアミノよりなる群から選択され、そして
R6およびR7はH、C1〜C5アルキル、フェニル、ベンジル、および4−ピリジニルよりなる群から選択されるが、ただし、R6またはR7の一方は4−ピリジニルであり、かつこのリガンドのR5〜R8における炭素の総数は4〜14である]
により表される銅錯体よりなる群から選択される請求項1に記載の方法。 - 銅前駆体が、構造(V)
[式中、
LはC2〜C15オレフィン、C2〜C15アルキン、ニトリル、芳香族複素環、およびホスフィンの群から選択され、
R1およびR4は独立して水素、メチル、エチル、プロピル、イソプロピル、イソブチル、ネオペンチルおよびC3〜C5アルキレンよりなる群から選択され、
R2、R3およびR5は独立して水素、フッ素、トリフルオロメチル、フェニル、C1〜C10アルキルおよびC3〜C5アルキレンよりなる群から選択されるが、ただし(R1、R2)および(R3、R4)の少なくとも一方は一緒になって−(CR6R7)n−、ここで、R6およびR7は独立して水素、フッ素、トリフルオロメチル、C1〜C5アルキル、C1〜C5アルキルエステルよりなる群から選択され、nは3、4または5である、である]
により表される銅錯体よりなる群から選択される請求項1に記載の方法。 - 表面活性化剤がプロトン源である請求項1に記載の方法。
- プロトン源が、イミンおよび芳香族窒素複素環よりなる群から選択される請求項8に記載の方法。
- 窒素複素環がピラゾールおよび置換ピラゾールよりなる群から選択される請求項9に記載の方法。
- 還元剤が、9−ボラビシクロ[3.3.1]ノナン、ジボラン、BRxH3−xの形態のボラン(式中、x=0、1または2であり、Rは独立してフェニルおよびC1〜C10アルキル基よりなる群から選択される)、ジヒドロベンゾフラン、ピラゾリン、ジシラン、SiR’yH4−yの形態のシラン、式中、y=0、1、2または3であり、R’は独立してフェニルおよびC1〜C10アルキル基よりなる群から選択される、およびGeR”zH4−zの形態のゲルマン、式中、z=0、1、2、または3であり、R”は独立してフェニルおよびC1〜C10アルキル基よりなる群から選択される、よりなる群から選択される請求項1に記載の方法。
- 還元剤が、9−ボラビシクロ[3.3.1]ノナン、ボラン、ジボラン、ジヒドロベンゾフラン、ピラゾリン、ゲルマン、ジエチルシラン、ジメチルシラン、エチルシラン、フェニルシラン、シランおよびジシランよりなる群から選択される請求項11に記載の方法。
- 基材が、銅、シリコン、二酸化ケイ素、低k基材、または銅の移行を防止するためのバリア層でコートされた低k基材よりなる群から選択される請求項1に記載の方法。
- バリア層が、タンタル、窒化タンタル、チタン、窒化チタン、窒化タンタル・シリコン、窒化チタン・シリコン、窒化タンタル・カーボン、炭窒化タングステン、および窒化ニオブよりなる群から選択される請求項13に記載の方法。
- 基材が銅錯体の蒸気に曝露される請求項1に記載の方法。
- 基材を表面活性化基に曝露した後であるが、基材上の表面活性化基の蒸着物を銅前駆体に曝露する前に、未蒸着表面活性化剤を除去するパージ工程をさらに含んでなる請求項1に記載の方法。
- 基材を表面活性化基に曝露した後であるが、基材上の表面活性化基の蒸着物を銅前駆体に曝露する前に、未蒸着表面活性化剤を除去する排出工程をさらに含んでなる請求項1に記載の方法。
- 蒸着された錯体を還元剤の蒸気に曝露する前に、未蒸着銅錯体を除去するパージ工程をさらに含んでなる請求項1に記載の方法。
- 蒸着された錯体を還元剤の蒸気に曝露する前に、排気またはパージによって未蒸着銅錯体を除去する排出工程をさらに含んでなる請求項1に記載の方法。
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US7488435B2 (en) | 2006-08-07 | 2009-02-10 | E. I. Du Pont De Nemours And Company | Copper(I) complexes and processes for deposition of copper films by atomic layer deposition |
WO2008018861A1 (en) * | 2006-08-07 | 2008-02-14 | E. I. Du Pont De Nemours And Company | Copper(i) complexes and processes for deposition of copper films by atomic layer deposition |
US20090130466A1 (en) * | 2007-11-16 | 2009-05-21 | Air Products And Chemicals, Inc. | Deposition Of Metal Films On Diffusion Layers By Atomic Layer Deposition And Organometallic Precursor Complexes Therefor |
WO2010132871A1 (en) | 2009-05-15 | 2010-11-18 | Wayne State University | Thermally stable volatile film precursors |
WO2012027357A2 (en) | 2010-08-24 | 2012-03-01 | Wayne State University | Thermally stable volatile precursors |
US9822446B2 (en) | 2010-08-24 | 2017-11-21 | Wayne State University | Thermally stable volatile precursors |
US20130330473A1 (en) * | 2012-06-11 | 2013-12-12 | Wayne State University | Atomic Layer Deposition of Transition Metal Thin Films Using Boranes as the Reducing Agent |
US8907115B2 (en) | 2012-12-10 | 2014-12-09 | Wayne State University | Synthesis and characterization of first row transition metal complexes containing α-keto hydrazonate ligands as potential precursors for use in metal film deposition |
US9758866B2 (en) | 2013-02-13 | 2017-09-12 | Wayne State University | Synthesis and characterization of first row transition metal complexes containing α-imino alkoxides as precursors for deposition of metal films |
US9157149B2 (en) | 2013-06-28 | 2015-10-13 | Wayne State University | Bis(trimethylsilyl) six-membered ring systems and related compounds as reducing agents for forming layers on a substrate |
US9249505B2 (en) | 2013-06-28 | 2016-02-02 | Wayne State University | Bis(trimethylsilyl) six-membered ring systems and related compounds as reducing agents for forming layers on a substrate |
WO2015099452A1 (ko) | 2013-12-24 | 2015-07-02 | 주식회사 유피케미칼 | 구리 금속 필름 및 이의 제조 방법, 및 이를 이용한 반도체 소자용 구리 배선의 형성 방법 |
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WO2003102266A1 (en) * | 2002-06-04 | 2003-12-11 | Applied Materials, Inc. | Deposition of copper films |
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