TWI343367B - Volatile copper(i) complexes for deposition of copper films by atomic layer deposition - Google Patents
Volatile copper(i) complexes for deposition of copper films by atomic layer deposition Download PDFInfo
- Publication number
- TWI343367B TWI343367B TW93110729A TW93110729A TWI343367B TW I343367 B TWI343367 B TW I343367B TW 93110729 A TW93110729 A TW 93110729A TW 93110729 A TW93110729 A TW 93110729A TW I343367 B TWI343367 B TW I343367B
- Authority
- TW
- Taiwan
- Prior art keywords
- group
- copper
- substrate
- independently selected
- phenyl
- Prior art date
Links
- 239000010949 copper Substances 0.000 title claims description 60
- 229910052802 copper Inorganic materials 0.000 title claims description 57
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 56
- 230000008021 deposition Effects 0.000 title claims description 3
- 238000000231 atomic layer deposition Methods 0.000 title description 12
- 238000000151 deposition Methods 0.000 title description 8
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical class [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 title description 5
- 239000000758 substrate Substances 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 32
- 239000002131 composite material Substances 0.000 claims description 30
- 239000003638 chemical reducing agent Substances 0.000 claims description 24
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 11
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 10
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 8
- 230000004888 barrier function Effects 0.000 claims description 7
- 150000004699 copper complex Chemical class 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 125000001495 ethyl group Chemical group [H]C([H])([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
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 229910052715 tantalum Inorganic materials 0.000 claims description 5
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 5
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 claims description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims description 4
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 4
- -1 copper imide copper complex Chemical class 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 239000004575 stone Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910000085 borane Inorganic materials 0.000 claims description 2
- 238000005256 carbonitriding Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 150000004767 nitrides Chemical class 0.000 claims description 2
- DNXIASIHZYFFRO-UHFFFAOYSA-N pyrazoline Chemical compound C1CN=NC1 DNXIASIHZYFFRO-UHFFFAOYSA-N 0.000 claims description 2
- 239000000779 smoke Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 3
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims 3
- 241000208125 Nicotiana Species 0.000 claims 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 claims 1
- 239000012327 Ruthenium complex Substances 0.000 claims 1
- 238000003723 Smelting Methods 0.000 claims 1
- SWSXFVZSWSXNIN-UHFFFAOYSA-J [Bi+4].[O-]P([O-])=O.[O-]P([O-])=O Chemical compound [Bi+4].[O-]P([O-])=O.[O-]P([O-])=O SWSXFVZSWSXNIN-UHFFFAOYSA-J 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical group 0.000 claims 1
- 239000011248 coating agent Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 claims 1
- OUFLLVQXSGGKOV-UHFFFAOYSA-N copper ruthenium Chemical compound [Cu].[Ru].[Ru].[Ru] OUFLLVQXSGGKOV-UHFFFAOYSA-N 0.000 claims 1
- KIWBPDUYBMNFTB-UHFFFAOYSA-M ethyl sulfate Chemical compound CCOS([O-])(=O)=O KIWBPDUYBMNFTB-UHFFFAOYSA-M 0.000 claims 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 claims 1
- 241000894007 species Species 0.000 claims 1
- 235000012431 wafers Nutrition 0.000 description 14
- 239000003446 ligand Substances 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 239000010408 film Substances 0.000 description 10
- 229910000071 diazene Inorganic materials 0.000 description 9
- 230000009467 reduction Effects 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000010409 thin film Substances 0.000 description 6
- 239000012691 Cu precursor Substances 0.000 description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 229910052707 ruthenium Inorganic materials 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 150000004696 coordination complex Chemical class 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-dimethylhexane Chemical group CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 description 2
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 230000005669 field effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000000877 morphologic effect Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- GTJOHISYCKPIMT-UHFFFAOYSA-N 2-methylundecane Chemical compound CCCCCCCCCC(C)C GTJOHISYCKPIMT-UHFFFAOYSA-N 0.000 description 1
- PKXHXOTZMFCXSH-UHFFFAOYSA-N 3,3-dimethylbut-1-ene Chemical compound CC(C)(C)C=C PKXHXOTZMFCXSH-UHFFFAOYSA-N 0.000 description 1
- JNXHRMHNWIOCQT-UHFFFAOYSA-N 3-ethyl-2,2-dimethylundecane Chemical compound CCCCCCCCC(CC)C(C)(C)C JNXHRMHNWIOCQT-UHFFFAOYSA-N 0.000 description 1
- RPDFRSKJKOQCIT-UHFFFAOYSA-N 3-ethyldodecane Chemical compound CCCCCCCCCC(CC)CC RPDFRSKJKOQCIT-UHFFFAOYSA-N 0.000 description 1
- WMXUIPXUVXNVKF-UHFFFAOYSA-N 4-(2-methylpropylamino)pent-3-en-2-one Chemical compound CC(C)CNC(C)=CC(C)=O WMXUIPXUVXNVKF-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- GTBNNXKMDOTJSM-UHFFFAOYSA-N C(=C)C(CCCCCCCCC)CCCCCCCCCC Chemical compound C(=C)C(CCCCCCCCC)CCCCCCCCCC GTBNNXKMDOTJSM-UHFFFAOYSA-N 0.000 description 1
- RDISCVBNNQSUDT-UHFFFAOYSA-N C(C)(C)(C)C(C=C)CCCCCCC Chemical compound C(C)(C)(C)C(C=C)CCCCCCC RDISCVBNNQSUDT-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 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
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- UEIGCUVBKYUAIJ-UHFFFAOYSA-N [Li]C(CCC)CCCC Chemical compound [Li]C(CCC)CCCC UEIGCUVBKYUAIJ-UHFFFAOYSA-N 0.000 description 1
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- JRBRVDCKNXZZGH-UHFFFAOYSA-N alumane;copper Chemical compound [AlH3].[Cu] JRBRVDCKNXZZGH-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000000277 atomic layer chemical vapour deposition Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- UZILCZKGXMQEQR-UHFFFAOYSA-N decyl-Benzene Chemical compound CCCCCCCCCCC1=CC=CC=C1 UZILCZKGXMQEQR-UHFFFAOYSA-N 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- WYACBZDAHNBPPB-UHFFFAOYSA-N diethyl oxalate Chemical compound CCOC(=O)C(=O)OCC WYACBZDAHNBPPB-UHFFFAOYSA-N 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- TZMFJUDUGYTVRY-UHFFFAOYSA-N ethyl methyl diketone Natural products CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- GPMBECJIPQBCKI-UHFFFAOYSA-N germanium telluride Chemical compound [Te]=[Ge]=[Te] GPMBECJIPQBCKI-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000011159 matrix material Substances 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
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/08—Copper compounds
-
- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31678—Of metal
- Y10T428/31681—Next to polyester, polyamide or polyimide [e.g., alkyd, glue, or nylon, etc.]
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Chemical Vapour Deposition (AREA)
- Electrodes Of Semiconductors (AREA)
Description
1343367 九、發明說明： 【發明所屬之技術領域】 本發明係關於新穎1，3-二亞胺銅複合物及在原子層沈積 方法中在基材上或在多孔固體内部或其上面沈積銅所用之 1，3-二亞胺銅複合物的應用。 【先前技術】 如 M. Ritala及 M_ Leskela於"Atomic Layer Deposition”， Handbook of Thin Film Materials，H. S. Nalwa，Editor， Academic Press ’ San Diego，2001年，第 1卷，第 2章中所 述，原子層沈積（ALD)方法適用於薄膜之創造。該等薄膜（尤 其金屬及金屬氧化物薄膜）係電子電路及裝置之製造的關 鍵元件。 在用於沈積銅薄膜之ALD方法中，交替將銅前驅體及還 原劑引入於反應腔室中。在將該銅前驅體引入於該反應腔 室中且允許其吸附於基材上之後，自該腔室抽汲或淨化過 量的（未吸附之）前驅體蒸汽。在此方法之後引入了與基材表 面上的該銅前驅體反應之還原劑以形成銅金屬及游離態配 位基。若需要，則可重複此循環以達成所要之薄膜厚度。 此方法與金屬複合物的分解化學中之化學氣相沈積 (C D)不1¾ SCVD方法中，該複合物一旦與表面接觸即分 解以產生所要之薄膜。在ALD方法中，複合物即使與表面 接觸’亦不會分解為金屬。相反地，該金屬薄膜之形成發 ;引第一忒4時，该第二試劑與該沈積金屬複合物發 生反應。自銅⑴複合物來製備銅薄膜時，該第二試劑為還 92625.doc 1343367 原劑。歸功於前驅體在該方法之第一步驟中對基材表面之 自限製吸附性，ALD方法之優勢包含對覆蓋範圍之薄膜厚 度及改良正形性（impr〇ved c〇nf〇rmality)進行控製的能力。 為了適用於ALD方法，銅複合物必須充分具有揮發性以 不產生熱分解即可汽化。通常使用含三氟甲基之配位基來 增加銅複合物之揮發性。然而，因為剩餘_化物對場效電 晶體之特性造成不利影響，所以此方法在該場效電晶體之 製備甲存在缺點。 用於該ALD方法之該等配位基亦必須對於分解穩定，且 能夠以金屬游離態自該複合物脫附。該配位基隨著銅之還 原而釋出’且必須自該表面移除以阻止其併入將要形成之 金屬層中。 US 5,464,666描述了 1，3-二亞胺銅複合物在氫之存在下進 行分解以形成銅。此專利案亦描述了 1，3 -二亞胺銅複合物在 用於產生銅鋁合金之化學氣相沈積方法中的應用。 DE 4202889描述了 1,3-二亞胺金屬複合物較佳藉由化學 氣相沈積方法來沈積塗層之應用。該金屬複合物在還原氣 氛（較佳為氩）中之分解亦得以揭示。 S.G. McGeachin 5 Canadian Journal of Chemistry, 46, 1903-1912( 1968)描述了 1，3·二亞胺及該等配位基的金屬複 合物之合成，該等金屬複合物包含形態ML22雙螯合劑或同 萊普提（homoleptic)複合物。 US 6,464,779揭示了 Cu原子層CVD方法，其需要以氧化 劑來處理含有氧及氟之銅前驅體以形成銅氧化物，繼而以 92625.doc 1343367 還原劑來處理該表面。 【發明内容】 本發明描述一種用於在基材上形成銅沈積物之方法，其 包括： a.使銅複合物（1)與基材接觸以在基材上形成銅複合物之沈 積物；及 ' R2 R1
(0 b.使還原劑與已沈積之銅複合物接觸，其中 L為包括2-15個碳之烯烴； R1及R4係獨立選自由氫、甲基、乙基、丙基、異丙美、 異丁基及新戊基組成之群； R2及R3係獨立選自由苯基及CrCw烷基組成之群；及 該還原劑係選自由下列各物組成之群：9_BBn(9_棚二環 [3.3.1]壬烷）；二硼烷；形態BRXH3.X之硼烷，其中χ=〇、i 或2，且R係獨立選自由苯基及Ci-C1Q燒基組成之群.二氮 苯幷吱喃；。比唾啉；二矽烷；形態SiR，yH4-yt碎燒，其中丫 =0、1、2或3’且RI係獨立選自由笨基及Ci_CiG烷基組成之 92625.doc 1343367 群；及形態GeR”zH4-z之鍺烷，其中z=〇、1、2或3，且汉" 係獨立選自由苯基及Cl_Cl()烷基組成之群。 【實施方式】 申請者已經發現適用於銅薄膜的創造之原子層沈積 (ALD)方法’該專銅薄膜在積體電路中之銅互連形成中用作 晶種層或用於裝飾或催化應用。此方法使用具有揮發性、 熱穩定性及衍生自僅由C、Η、Si及N組成的配位基之銅（1) 複合物。選擇s亥导配位基以形成雖然在適當的溫度範圍内 具揮發性但在此溫度範圍内不會分解為銅金屬之銅⑴複合 物；相反地，該等複合物在添加適當的還原劑時分解為金 屬。進一步選擇該等配位基以使得其在該銅複合物暴露於 還原劑時將不分解即脫附。已經證明藉由易得之還原劑所 進行的該等銅複合物至銅金屬之還原係在適中溫度下清潔 地進行。 在本發明之方法中，藉由以下步驟在基材上沈積銅： a.使基材與銅複合物（I)接觸以在該基材上形成銅複合物之 沈積物；及
92625.doc 1343367 b‘使所沈積之鋼複合物與還原劑接觸，其中 L為包括2 -〗5個碳之稀煙；
Rl及R4係獨立選自由氫、甲基、乙基、丙基、異丙基、 異丁基及新戊基組成之群； V及W係獨立選自由苯基及Ci;絲組成之群，·及 該還原劑係選自由下列各物組成之群：9·ΒΒΝ;二蝴烧； BRxH3-x形態之硼院，其中Ρ0叫或2,且R係獨立選自由 苯基及CrC丨。烷基組成之群；二氫苯幷呋喃；吡唑啉；二矽 烷;SiRU)態之石夕烷，其中广〇、丨、2或3，Μ，係獨 立選自由本基及Cl_C|。烷基組成之群；及GeR"u態之 鍺烧’其中Z=〇、l、2戎3B本， 日寻且R係獨立選自由笨基與Ci_Cw 烷基組成之群。 本發明之沉積方法因為可使用較低溫度且產生較高品 質、更均句之薄膜’而較技術界所述方法改#。本發明之 該方法亦提供得到銅薄膜之更直接路徑，以避免中間氧化 物薄膜之形成。 在本發明之㈣沈積方法中，銅可沉積在該基材之表面 上或在其夕孔結構之内部或表面。適當之基材包含導電、 半導電及，、€緣基材’其包含以障壁層所塗佈之銅、碎晶圓、 用於超大規模積體電路製造中之晶圓、以具有比二氧化矽 低的"電*數之介電材料所製備之晶圓及二氧化矽及低让 基材。阻止銅漂移之障壁層包含纽、1化組、鈦、氮化欽、 氮化钽矽、氮化鈦矽、碳氮化钽及氤化鈮。 此方法可在溶液中進行，意即藉由使該銅複合物之溶液 92625.doc -10· 1343367 與該還原顯觸H最好使該基材暴露於該銅複合物 之瘵/飞’且隨後在使已沈積之複合物暴露於該還原劑的蒸 汽之前藉由真空或淨化來移除任何過量的銅複合物（意即 未沈積之複合物P在該銅複合物之還原以後，可藉由真 空、淨化、加熱、以適當溶劑漂洗或該等步驟之組合來移 除游離態該配位基。 可重複此方法以逐步建立銅之較厚層或消除孔洞。 該銅複合物之沈積通常在0至200。(：下進行。該銅複合物 之還原通常在類似溫度（0至20(rc)下進行。 在本發明之方法中’最初銅複合物沈積於該基材上。在 該銅複合物暴露於該還原劑之前不會出現金屬銅薄膜之形 成。 需要侵蝕性還原劑以迅速且完全地還原該銅複合物。還 原劑必須具揮發性且在加熱時不分解。其亦必須具有足夠 還原能力以在與沈積於該基材表面上之該銅複合物接觸時 k速反應。已經識別了一組以前未用於方法中銅⑴還 原之適當的還原劑。該等試劑之—個特徵為質子供體之存 在。該試劑必須能夠轉移至少—個電子以還原該複合物之 銅離子及至少―個質子以使該配位基質子化。必須能夠自 遠新形成的鋼沈積物之表面容易地移除該經氧化之還原劑 及該質子化之配位基。 用於本發明的該銅沈積方法之適當還原劑包含9_BBN、 m笨、鍺烧、二乙基石夕 烷、二甲基矽烷、乙基矽烷、苯基矽烷、矽烷及二矽烷。 92625.doc 1343367 二乙基石夕烧及石夕烧為較佳。
在該銅沈積方法之一實施例中’於溫度、時間及壓力條 件下將該銅複合物添加於一反應器中以達到複合物至該基 材表面之適當積分通量《熟習此項技術者應瞭解該等變量 之選擇將取決於個別腔室與系統設計及所要之處理速率。 在至少一部分該銅複合物已沈積於該基材上（如經塗佈之 石夕晶圓）以後，自該腔室抽汲或淨化該未沈積之複合物蒸汽 且以大約50至760毫托（mT〇rr)之壓力將該還原劑弓丨入於該 腔室中以還原該經吸附之銅複合物。在還原期間使該基材 保持於大約0至20(TC之間之溫度。隨著鋼複合物及還原劑 之適s組合，此還原迅速且完全。還原劑暴露時間可為少 於一秒鐘至若干分鐘^重要的是該反應之產物在該等還原 條件下容易自該基材表面移除。
在本發明之一實施例中，該銅複合物為銅1，3-二亞胺複合 物（1)’其中R|及R4為異丁基，R2及R3為曱基，且乙烯基 一甲基石夕烧，且該還原劑為二乙基石夕烧。 本發明亦提供新穎丨，3-二亞胺銅複合物（I)，
92625.doc -12- (0 1343367 其中L為包括2-15個碳之稀烴； R1及R4係獨立選自由氫、甲基、乙基、丙基 '異丙基、 異丁基及新戊基組成之群；且 R2及R3係獨立選自由苯基及Cl_ClG烷基組成之群。 在一實施例中，L為直鏈末端烯烴。關於4_15個碳之烯 烴，L亦可為順式或反式構型之内烯烴；順式為較佳。^可 為環狀或雙環狀烯烴亦可由如甲矽烷基來取代。適當之 烯烴包含乙烯基三甲基矽烷、烯丙基三甲基矽烷、丨已烯、 4_甲基-1-戊烯、3，3-二甲基-1-丁烯及降冰片烯。 以下實例1提供了適用於製作本發明的該銅複合物之一 特定配位基之合成。其它配位基同樣可自類似之胺基銅來 製備。 在另一實施例令，本發明提供了包括沈積於基材上的〖，3_ 二亞胺銅複合物（I)之物品。適當之基材包含：以障壁層所 塗佈之銅、矽晶圓、用於超大規模積體電路製造中之晶圓、 以具有比二氧化矽低的介電常數之介電材料所製備之晶圓 及二氧化碎及低k基材。障壁層可用於阻止銅漂移。適當之 障壁層包含：钽' 氮化钽、鈦、氮化鈦、氮化钽矽、氮化 鈥石夕、碳氮化組及氮化銳。 實例 所有有機試劑均可自Sigma-Aldrich Corporation (Milwaukee, Wl，USA)獲得。[Cu(CH3CN)4]S03CF3 可根據 Τ. Ogura，Transition Metal Chemistry，1，179-182(976)所述之 方法來製備》 92625.doc -13- 1343367 實例1 乙稀基三甲基矽烷（Ν,Ν，-二異丁基-2,4-戊二酮亞胺）銅之 製備及還原 在氮氣氛下之乾燥箱中，將4-(異丁基胺基）_3_戊烯_2_酮 (36.9 g，237 mmole)及硫酸二甲酯（3〇.〇 g，237 mmole)饋入 250 mL圓底燒瓶中。將該反應溶液攪拌5分鐘，且隨後不攪 拌’使其整夜靜置。該黃色混合物變成橙色且黏稠。藉由 附加漏斗來添加異丁胺（18 g，246 mmole)，同時劇烈搜拌。 將該溶液襻拌一小時直至其凝固。不分離中間鹽，而依下 述方式直接轉化為游離胺（基於該中間鹽之理論產量）。 將 NaOMe(12.8 g，237 mmole)之 MeOH(大約 40 mL)溶液 添加於該中間鹽且攪拌一小時。在真空下移除該溶劑以產 生黃色油，該黃色油以戊烷萃取、過濾及濃縮，以產生基 於質子NMR資料確定由所要產物（Ν，Ν，_二異丁基_2,私戊二 酮亞胺）（大約75〇/〇)及未反應起始材料（大約25%)所組成之 百色油。藉由分館來分離該產物以產生黃色油（35 4 g，72〇/〇 產率）。 在該乾燥箱中，將[Cu(CH3CN)4]s〇3CF3(1 〇 g)、乙烯基 二曱基矽烷（26.0 mmole)及二乙醚（2〇 mL)饋入100-mL圓底 燒瓶中。在另一個1 〇〇_mL圓底燒瓶中，將15M的第三丁基 鋰（1.7 mL)添加於如上述所製備之N，N，_二異丁基-2,4•戊二 酮亞胺（0.550 g)+。〇.5小時以後，结合該等溶液。在吸收 所有固體以後，該經結合之溶液由渾濁白色懸浮液變為金 育褐色澄清溶液。2小時以後，將該溶液濃縮為固體/淤渣、 92625.doc 14
以戊烷（3 x M mT )卒取、過濾及濃縮以產生黏稠油（〇 6〇〇 g ’ 62%產率）。 實例2 、將作為實例1之最終產物來分離之黏性油用作銅前驅體 ^在基材上創造㈣膜。該基材由具有25G.A的is層及100 的銅層之—氧化石夕晶圓組成。該晶圓具有幾乎無法辨別之 鋼色。 在乾燥相中將大約0·040 g之銅前驅體加載於曼製船形器 中將違船形器皿及晶圓（約丨cm2)大約相隔3 5英吋置放 於玻璃官中。自該乾燥箱中移除該玻璃管，且將其連接 至一真空管線。將加熱旋管附著於圍繞該瓷製船形器皿周 圍域及該晶圓片周圍域之該玻璃管；此構型允許此兩個區 域保持不同溫度。隨著該系統之排空創造出通過該管之氬 流’其首先通過該船形器皿中之樣品且隨後通過該晶圓。 在該管内部之壓力保持在15〇·2〇〇毫托。將該晶圓周圍之區 域加熱至11 (TC。大約1小時以後’該樣品船形器皿周圍之 區域的溫度上升至55t。將該等溫度及該Ar氣體流保持約 2.5小時。隨後’將該樣品船形器皿周圍域冷卻至室溫。將 該管排空至約1〇毫托之壓力，且以二乙基矽烷反填充。在 11 〇°C之該管域迅速變為銅色。冷卻該裝置，且將其返回至 或乾燥箱。感覺該銅色較暗。重複該方法以產出具有平滑 金屬銅薄膜之晶圓。 92625.doc •15-
Claims (1)
- 1343367 第093110729號專利申請案 中文申請專利範圍替換本(99年1 十、申請專利範圍： 一種用於在基材上形成銅沈積物之方法其包括： a.使基材與銅複合物⑴接觸以在該基材上形成銅複合物 之沈積物；及 R2 R10) b.使所沈積之銅複合物與還原劑接觸，其中 L為包括2 -1 5個碳之稀煙； R1及R4係獨立選自由氫、甲基、乙基、丙基、異丙基、 異丁基及新戊基組成之群； R2及R3係獨立選自由苯基及CrCW基組成之群；及 該還原劑係選自由以下各物組成之群：9硼二環[3 3 u 壬烷（9-BBN),二硼烷；BRxh3 x形態之硼烷，其中χ = 〇、1或2，且R係獨立選自由苯基及Ci C^烷基组成之 群，一氫苯幷呋喃；吡唑啉；二矽烷；SiR，yH4 y形態之 矽院’其中3^0、1、2或3，且R·係獨立選自由苯基及 Cl_Cl0烷基組成之群；及GeR，，zH4_z形態之鍺烷，其中z 二〇、卜2或3’且R，·係獨立選自由苯基及c广Ci〇烷基組 成之群。 92625-990113.doc 7LJ4JJ0/ 其中R2及R3為甲基，且Ri 其中L為乙烯基三甲基石夕 其申該基材係選自由以障 氧化矽組成之群。 其中該基材係暴露於該銅 2·如申請專利範圍第1項之方法 及R4為異丁基。 3.如申請專利範圍第丨項之方法 烷。 ' 4. 如申請專利範圍第】項之方法 壁層所塗佈之銅、矽晶圓及二 5. 如申請專利範圍第1項之方法 複合物之蒸汽下。6·如申請專利範圍第1項之方法 下進行。 其中該沈積係在〇至2〇〇°c 其中該還原劑係為石夕烧或 7.如申請專利範圍第丨項之方法 一乙基碎烧。 8’ 種1,3 - 一亞胺銅複合物（!），其中 L為包括2-15個碳之烤煙； R及R4係獨立選自由氫、甲基 '乙基、丙基 '異丙基、 異丁基及新戊基組成之群； 92625-990113.doc R2及R3係獨立選自由苯基及Ci_Cig烷基組成之群。 9.如申請專利範圍第8項之〗，弘二亞胺銅複合物，其令 L為乙缔基三τ基石夕烧； R1及R4係選自由氫、異丁基及新戊基組成之群； R2為甲基；及 R係選自由f基、乙基及笨基組成之群。 10.—種藉由使基材與如申請專利範圍第8項之〗，3•二亞胺銅 複σ物接觸所製得之物品’其係於該基材上形成該銅複 合物之沈積。 如申請專利範圍第10項之物品，其中該基材係選自由塗 佈有障壁層之銅、矽晶圓及二氧化矽組成之群。 如申請專利範圍第u項之物品，其中該障壁層係選自由 钽、氮化鈕、鈦、氮化鈦、氮化鉅矽、氮化鈦矽、碳氮 化组及氮化銳組成之群。 92625-990113.doc
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| JP2005520053A (ja) * | 2002-01-18 | 2005-07-07 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | 原子層堆積によって銅薄膜を堆積させるための揮発性銅（ｉｉ）錯体 |
| US20050227007A1 (en) * | 2004-04-08 | 2005-10-13 | Bradley Alexander Z | Volatile copper(I) complexes for deposition of copper films by atomic layer deposition |
| KR20070048215A (ko) * | 2004-07-30 | 2007-05-08 | 이 아이 듀폰 디 네모아 앤드 캄파니 | 원자층 침착에 의한 구리 막의 침착용 구리（ⅱ） 착물 |
| US7034169B1 (en) | 2004-12-30 | 2006-04-25 | Air Products And Chemicals, Inc. | Volatile metal β-ketoiminate complexes |
| US7205422B2 (en) | 2004-12-30 | 2007-04-17 | Air Products And Chemicals, Inc. | Volatile metal β-ketoiminate and metal β-diiminate complexes |
| US7572731B2 (en) * | 2005-06-28 | 2009-08-11 | Micron Technology, Inc. | Unsymmetrical ligand sources, reduced symmetry metal-containing compounds, and systems and methods including same |
| US7416994B2 (en) * | 2005-06-28 | 2008-08-26 | Micron Technology, Inc. | Atomic layer deposition systems and methods including metal beta-diketiminate compounds |
| US7439338B2 (en) * | 2005-06-28 | 2008-10-21 | Micron Technology, Inc. | Beta-diketiminate ligand sources and metal-containing compounds thereof, and systems and methods including same |
| 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 |
| US8263795B2 (en) * | 2007-11-05 | 2012-09-11 | Air Products And Chemicals, Inc. | Copper precursors for thin film 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 |
| DE102007058571B4 (de) * | 2007-12-05 | 2012-02-16 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Substrat mit einer Kupfer enthaltenden Beschichtung und Verfahren zu deren Herstellung mittels Atomic Layer Deposition und Verwendung des Verfahrens |
| WO2020011637A1 (en) * | 2018-07-12 | 2020-01-16 | Basf Se | Process for the generation of metal- or semimetal-containing films |
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| DE4202889C2 (de) * | 1992-02-01 | 1994-12-15 | Solvay Deutschland | Verfahren zur Abscheidung von ein Metall der ersten Übergangsmetallreihe oder Aluminium enthaltenden Schichten und 1,3-Diketiminato-Metall-Verbindungen |
| US5464666A (en) * | 1995-02-06 | 1995-11-07 | Air Products And Chemicals, Inc. | Process for chemical vapor codeposition of copper and aluminum alloys |
| KR100225686B1 (ko) * | 1995-03-20 | 1999-10-15 | 모리시다 요이치치 | 막형성용 재료 및 배선형성방법 |
| US6511936B1 (en) * | 1998-02-12 | 2003-01-28 | University Of Delaware | Catalyst compounds with β-diminate anionic ligands and processes for polymerizing olefins |
| US6281124B1 (en) * | 1998-09-02 | 2001-08-28 | Micron Technology, Inc. | Methods and systems for forming metal-containing films on substrates |
| EP1264817A1 (en) * | 2000-03-14 | 2002-12-11 | Nissan Chemical Industries, Ltd. | $g(b)-DIKETONATOCOPPER(I) COMPLEX CONTAINING ALLENE COMPOUND AS LIGAND AND PROCESS FOR PRODUCING THE SAME |
| JP2001328953A (ja) * | 2000-03-14 | 2001-11-27 | Nissan Chem Ind Ltd | アレン化合物を配位子としたβ−ジケトネート銅（Ｉ）錯体およびその製造法 |
| US20020013487A1 (en) * | 2000-04-03 | 2002-01-31 | Norman John Anthony Thomas | Volatile precursors for deposition of metals and metal-containing films |
| US6464779B1 (en) * | 2001-01-19 | 2002-10-15 | Novellus Systems, Inc. | Copper atomic layer chemical vapor desposition |
| US6821891B2 (en) * | 2001-11-16 | 2004-11-23 | Applied Materials, Inc. | Atomic layer deposition of copper using a reducing gas and non-fluorinated copper precursors |
| JP2005520053A (ja) * | 2002-01-18 | 2005-07-07 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | 原子層堆積によって銅薄膜を堆積させるための揮発性銅（ｉｉ）錯体 |
| US20050227007A1 (en) * | 2004-04-08 | 2005-10-13 | Bradley Alexander Z | Volatile copper(I) complexes for deposition of copper films by atomic layer deposition |
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| KR101132444B1 (ko) | 2012-03-30 |
| US20060182884A1 (en) | 2006-08-17 |
| CN1774523A (zh) | 2006-05-17 |
| KR20060010746A (ko) | 2006-02-02 |
| WO2004094689A2 (en) | 2004-11-04 |
| US20040247905A1 (en) | 2004-12-09 |
| WO2004094689A3 (en) | 2005-01-20 |
| DE602004018627D1 (de) | 2009-02-05 |
| TW200500327A (en) | 2005-01-01 |
| JP2006523778A (ja) | 2006-10-19 |
| EP1613789B1 (en) | 2008-12-24 |
| JP4649402B2 (ja) | 2011-03-09 |
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