US20110293830A1 - Precursors and methods for atomic layer deposition of transition metal oxides - Google Patents
Precursors and methods for atomic layer deposition of transition metal oxides Download PDFInfo
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- US20110293830A1 US20110293830A1 US13/034,564 US201113034564A US2011293830A1 US 20110293830 A1 US20110293830 A1 US 20110293830A1 US 201113034564 A US201113034564 A US 201113034564A US 2011293830 A1 US2011293830 A1 US 2011293830A1
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- United States
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- metal
- cht
- transition metal
- reactants
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 99
- 238000000231 atomic layer deposition Methods 0.000 title claims abstract description 45
- 229910000314 transition metal oxide Inorganic materials 0.000 title claims abstract description 16
- 239000002243 precursor Substances 0.000 title claims description 97
- 239000000376 reactant Substances 0.000 claims abstract description 175
- CHVJITGCYZJHLR-UHFFFAOYSA-N cyclohepta-1,3,5-triene Chemical compound C1C=CC=CC=C1 CHVJITGCYZJHLR-UHFFFAOYSA-N 0.000 claims abstract description 110
- 239000003446 ligand Substances 0.000 claims abstract description 51
- 239000010409 thin film Substances 0.000 claims abstract description 45
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 37
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 37
- 125000002188 cycloheptatrienyl group Chemical group C1(=CC=CC=CC1)* 0.000 claims abstract description 32
- 229910052751 metal Inorganic materials 0.000 claims description 94
- 239000002184 metal Substances 0.000 claims description 94
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 61
- 229910052760 oxygen Inorganic materials 0.000 claims description 58
- 239000001301 oxygen Substances 0.000 claims description 58
- 239000000758 substrate Substances 0.000 claims description 56
- 238000006243 chemical reaction Methods 0.000 claims description 55
- 239000010936 titanium Substances 0.000 claims description 44
- 229910052723 transition metal Inorganic materials 0.000 claims description 36
- 239000010408 film Substances 0.000 claims description 33
- 150000003624 transition metals Chemical class 0.000 claims description 33
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 32
- 125000000217 alkyl group Chemical group 0.000 claims description 32
- 229910052735 hafnium Inorganic materials 0.000 claims description 31
- 229910052719 titanium Inorganic materials 0.000 claims description 31
- 229910052726 zirconium Inorganic materials 0.000 claims description 29
- 239000012808 vapor phase Substances 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 21
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 16
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 13
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 9
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 8
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 8
- 239000006227 byproduct Substances 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 8
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 8
- 239000011541 reaction mixture Substances 0.000 claims description 8
- 239000002356 single layer Substances 0.000 claims description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 7
- JCXJVPUVTGWSNB-UHFFFAOYSA-N Nitrogen dioxide Chemical compound O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 claims description 7
- 125000002524 organometallic group Chemical group 0.000 claims description 7
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 6
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 5
- 230000002194 synthesizing effect Effects 0.000 claims description 5
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical group Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 5
- 229910021381 transition metal chloride Inorganic materials 0.000 claims description 5
- 229910003074 TiCl4 Inorganic materials 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000004767 nitrides Chemical class 0.000 claims description 4
- 125000002015 acyclic group Chemical group 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- 150000004820 halides Chemical class 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 229910001510 metal chloride Inorganic materials 0.000 claims 2
- 125000003331 eta(1)-cyclohepta-2,4,6-trienyl group Chemical group [H]C1([*])C([H])=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 1
- -1 integrated circuits Substances 0.000 abstract description 8
- 239000004065 semiconductor Substances 0.000 abstract description 5
- 239000003990 capacitor Substances 0.000 abstract description 4
- 238000000151 deposition Methods 0.000 description 48
- 230000008021 deposition Effects 0.000 description 40
- 230000008569 process Effects 0.000 description 28
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 12
- 238000010926 purge Methods 0.000 description 12
- 239000010410 layer Substances 0.000 description 11
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
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- 230000008901 benefit Effects 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 6
- 229910001928 zirconium oxide Inorganic materials 0.000 description 6
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 5
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 5
- 229910000449 hafnium oxide Inorganic materials 0.000 description 5
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 5
- 239000002052 molecular layer Substances 0.000 description 5
- 239000001272 nitrous oxide Substances 0.000 description 5
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 125000000547 substituted alkyl group Chemical group 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000004009 13C{1H}-NMR spectroscopy Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000012159 carrier gas Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910001507 metal halide Inorganic materials 0.000 description 3
- 150000005309 metal halides Chemical class 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 150000002902 organometallic compounds Chemical class 0.000 description 3
- 238000000859 sublimation Methods 0.000 description 3
- 230000008022 sublimation Effects 0.000 description 3
- 238000006557 surface reaction Methods 0.000 description 3
- 238000001757 thermogravimetry curve Methods 0.000 description 3
- 235000012431 wafers Nutrition 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- QOXHZZQZTIGPEV-UHFFFAOYSA-K cyclopenta-1,3-diene;titanium(4+);trichloride Chemical compound Cl[Ti+](Cl)Cl.C=1C=C[CH-]C=1 QOXHZZQZTIGPEV-UHFFFAOYSA-K 0.000 description 2
- 238000005137 deposition process Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001341 grazing-angle X-ray diffraction Methods 0.000 description 2
- 230000000155 isotopic effect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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- 230000003287 optical effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
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- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 238000004639 Schlenk technique Methods 0.000 description 1
- 229910003087 TiOx Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000003877 atomic layer epitaxy Methods 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- MKNXBRLZBFVUPV-UHFFFAOYSA-L cyclopenta-1,3-diene;dichlorotitanium Chemical compound Cl[Ti]Cl.C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 MKNXBRLZBFVUPV-UHFFFAOYSA-L 0.000 description 1
- YMNCCEXICREQQV-UHFFFAOYSA-L cyclopenta-1,3-diene;titanium(4+);dichloride Chemical compound [Cl-].[Cl-].[Ti+4].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 YMNCCEXICREQQV-UHFFFAOYSA-L 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- AASUFOVSZUIILF-UHFFFAOYSA-N diphenylmethanone;sodium Chemical compound [Na].C=1C=CC=CC=1C(=O)C1=CC=CC=C1 AASUFOVSZUIILF-UHFFFAOYSA-N 0.000 description 1
- 238000001678 elastic recoil detection analysis Methods 0.000 description 1
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- 238000002474 experimental method Methods 0.000 description 1
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- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 238000004636 glovebox technique Methods 0.000 description 1
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- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
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- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
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- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- HLLICFJUWSZHRJ-UHFFFAOYSA-N tioxidazole Chemical compound CCCOC1=CC=C2N=C(NC(=O)OC)SC2=C1 HLLICFJUWSZHRJ-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- IYQYZZHQSZMZIG-UHFFFAOYSA-N tricyclo[5.2.1.0(2.6)]deca-3,8-diene, 4.9-dimethyl Chemical compound C1C2C3C=C(C)CC3C1C=C2C IYQYZZHQSZMZIG-UHFFFAOYSA-N 0.000 description 1
- 238000007514 turning Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
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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
- C23C16/22—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 inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
- C23C16/405—Oxides of refractory metals or yttrium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/07—Producing by vapour phase processes, e.g. halide oxidation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
- C01G25/02—Oxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G27/00—Compounds of hafnium
- C01G27/02—Oxides
-
- 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
- C07F17/00—Metallocenes
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- 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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
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- 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
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- 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
- C23C16/45536—Use of plasma, radiation or electromagnetic fields
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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]
- C23C16/45553—Atomic layer deposition [ALD] characterized by the use of precursors specially adapted for ALD
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
Definitions
- the invention claimed herein was made by, or on behalf of, and/or in connection with a joint research agreement between the University of Helsinki and ASM Microchemistry Oy signed on Nov. 14, 2003 and renewed in 2008. The agreement was in effect on and before the date the claimed invention was made, and the claimed invention was made as a result of activities undertaken within the scope of the agreement.
- the present application relates generally to methods and compositions for depositing transition metal oxide thin films, such as titanium, zirconium and hafnium oxide thin films, by atomic layer deposition using metalorganic precursors.
- the metalorganic precursors comprise at least one cycloheptatriene (CHT) ligand.
- Atomic layer deposition is a self-limiting process, whereby alternated pulses of reactants saturate a substrate surface.
- the deposition conditions and precursors are selected such that an adsorbed layer of precursor in one pulse leaves a surface termination that is non-reactive with the gas phase reactants of the same pulse.
- a subsequent pulse of different reactants reacts with the previous termination to enable continued deposition.
- each cycle of alternated pulses typically leaves no more than about one molecular layer of the desired material.
- the principles of ALD type processes have been presented by T. Suntola, e.g. in the Handbook of Crystal Growth 3, Thin Films and Epitaxy, Part B: Growth Mechanisms and Dynamics, Chapter 14, Atomic Layer Epitaxy, pp.
- ALD processes can be used to deposit films at lower temperatures, typically CVD processes have been used for higher temperature growth because the reactions occur more rapidly at higher temperatures.
- some ALD processes can lose their self limiting nature at high temperatures. In some cases, higher temperatures can cause undesirable decomposition of some precursors. Some precursor decomposition can disrupt the self limiting nature of the ALD process, for example if the products of the decomposition reaction react with each other and/or react with the adsorbed species to deposit material on the substrate surface.
- Atomic layer deposition (ALD) of Group IVB metal oxides has been studied for years. However, higher temperature ALD options for these metal oxides are quite limited. Metal halide reactants are typically used; however, metal halides are incompatible with some materials and processes. Some metal-organic precursors have also been used. However, these reactants have not been well suited for higher temperature deposition processes.
- transition metal oxide thin films on a substrate in a reaction chamber by atomic layer deposition using metalorganic reactants.
- Organometallic reactants are used in some embodiments.
- the transition metal oxide thin films are Group IVB metal oxide thin films.
- the methods comprise providing a vapor phase pulse of a first reactant comprising a first Group IVB metalorganic precursor to a reaction chamber such that it forms no more than a monolayer on a substrate in the reaction chamber; removing excess first reactant from the reaction chamber; providing a vapor phase pulse of a second reactant comprising oxygen to the reaction chamber such that it converts the adsorbed Group IVB metal reactant to a metal oxide; and removing excess second reactant and any reaction byproducts from the reaction chamber.
- the providing and removing steps are repeated until a thin metal oxide film of a desired thickness and composition is obtained.
- the substrate temperature during the providing and removing steps may be above about 300° C., more preferably above about 350° C.
- the metalorganic precursor is an organometallic precursor, comprising a carbon-metal bond.
- methods for forming transition metal oxide films, preferably Group IVB metal oxide films, by atomic layer deposition comprise alternately and sequentially contacting a substrate with vapor phase pulses of a cycloheptatrienyl or cycloheptatriene (CHT) metal reactant and an oxygen source. The alternate and sequential pulses are repeated until a thin film of a desired thickness is obtained.
- CHT cycloheptatrienyl or cycloheptatriene
- CHT metal reactants are metalorganic, typically organometallic compounds, comprising at least one chycloheptatrienyl or cycloheptatriene ligand (a CHT ligand).
- the CHT metal reactant comprises only two ligands, including at least one cycloheptatrienyl or cycloheptatriene (CHT) ligand.
- the CHT metal reactant comprises two CHT ligands.
- the CHT metal reactant comprises two cycloheptatrienyl ligands.
- the CHT metal reactant comprises one CHT ligand and one cyclopentadienyl ligand (Cp).
- the CHT reactant does not comprise a halide. In some embodiments, the CHT reactant comprises one cycloheptadienyl (CHD) ligand. In some embodiments, the CHT reactant comprises two C 7 H 8 cycloheptatriene ligands.
- CHD cycloheptadienyl
- a CHT metal reactant is selected from the group consisting of reactants of the formula:
- a CHT metal reactant is selected from the group consisting of reactants of the formula:
- a CHT metal reactant is selected from the group consisting of reactants of the formula:
- a CHT metal reactant is selected from the group consisting of reactants of the formula:
- a CHT metal reactant is selected from the group consisting of reactants of the formula:
- a CHT metal reactant can take different forms depending on the conditions.
- a CHT metal reactant may have formula (V) under some conditions, but may be in the form of formula (VI) under other conditions.
- the compound in the formulas (I)-(VI) CHT, CHD or X, denote the structure of the ligand i.e. C 7 ring structure with double bonds or delocalized electrons, where different groups R 1 -R 16 can attach.
- the compound can be C 7 H 7 -M-L or ((CH 3 ) 3 C 7 H 4 )-M-L, not H 7 C 7 H 7 -M-L or (H 4 (CH 3 ) 3 C 7 H 7 )-M-L, respectively.
- transition metal nitride thin films are deposited by ALD using a transition metal CHT reactant and a nitrogen containing reactant.
- the metal CHT reactant comprises two CHT ligands.
- the CHT reactant does not comprise a Cp group.
- the CHT reactant comprises two C 7 H 8 cycloheptatriene ligands.
- transition metal carbide thin films such as Group IVB metal carbide films
- metal CHT reactant comprises two CHT ligands.
- the CHT reactant does comprise two C 7 H 8 cycloheptatriene ligands.
- methods of synthesizing transition metal precursors comprising one or more CHT ligands are provided.
- methods of synthesizing (C 7 H 8 )M(C 7 H 8 ), where M is a transition metal, preferably a Group IVB metal are provided.
- the methods may comprise forming a reaction mixture by combining a transition metal reactant with ferric chloride, cycloheptatriene and tetrahydrofuran (THF) in a flask containing magnesium chips.
- the transition metal reactant may be, for example, a Group IVB transition metal reactant, preferably a metal halide. Exemplary reactants include transition metal chlorides.
- the transition metal reactant is TiCl 4 .
- FIG. 1 shows the structure of CpTiCHT (left) and (MeCp)ZrCHT (right).
- FIG. 2 shows the TGA curves measured for CpTiCHT and (MeCp)ZrCHT.
- FIG. 3 is a graph of growth rate at various temperatures (top) and a graph of saturation as measured by growth rate for different metal reactant pulse lengths (bottom).
- FIG. 4 shows TofERDA data for ZrO 2 films deposited using (MeCp)ZrCHT and O 3 at various temperatures.
- FIGS. 5 a , 5 b and 5 c show XRD data for ZrO 2 films deposited using (MeCp)ZrCHT and O 3 at various temperatures.
- FIG. 6 represents graphs of GIXRD data for ZrO 2 films deposited using (MeCp)ZrCHT and O 3 .
- FIG. 7 illustrates experiments to characterize the electrical properties of ZrO 2 films deposited using (MeCp)ZrCHT and O 3 .
- FIG. 8 is a flow chart of an embodiment of an ALD process for depositing a Group IVB metal oxide using a CHT metal precursor.
- FIG. 9 is a schematic of the crystal structure of Ti(C 7 H 8 ) 2 .
- the formulation may also be (C 7 H 7 )Ti(C 7 H 9 ) i.e. (CHT)Ti(CHD).
- FIG. 10 shows TG, DTG and SDTA curves measured for (CHT)Ti(CHD).
- transition metal oxide films using metalorganic precursors are described herein. While primarily illustrated in the context of forming Group IVB metal oxide films, other transition metals can be substituted for the Group IVB metals in some embodiments, as will be recognized by the skilled artisan.
- the thin films are generally described with respect to the formation of an integrated circuit, such as a capacitor or transistor, the skilled artisan will readily appreciate the application of the principles and advantages disclosed herein to various contexts in which metal oxide thin films are useful. For example, transparent titanium oxide films can be used in flat panel displays, LEDs, and solar cells.
- transition metal nitride or metal carbide films such as Group IVB metal nitride and carbide films, can be deposited by ALD using the disclosed metal precursors.
- metal oxide film refers to a transition metal oxide film unless otherwise stated.
- Preferred transition metal oxide films are Group IVB metal oxide films.
- Group IVB metal oxide thin films include oxide films comprising titanium (Ti), zirconium (Zr) and/or hafnium (Hf).
- Exemplary Group IVB metal oxide films that are specifically discussed herein include TiO 2 , ZrO 2 and HfO 2 .
- Other Group IVB metal oxide films will be apparent to the skilled artisan.
- the Group IVB metals can be substituted with other transition metals, as will be understood by the skilled artisan.
- transition metal oxide films are deposited on a substrate by atomic layer deposition (ALD) type processes utilizing one or more metalorganic precursors.
- the metalorganic precursor is an organometallic precursor and thus comprises a carbon-metal bond.
- deposition temperatures of greater than 300° C. are used. In other embodiments, deposition temperatures of greater than 350° C. are used.
- CHT metal reactants are utilized.
- CHT metal reactants are metal reactants comprising at least one CHT ligand.
- the CHT metal reactant may be a metalorganic compound and in some embodiments is an organometallic compound.
- CHT ligands are cycloheptatrienyl and cycloheptatriene ligands.
- CHT metal reactants comprise at least one cycloheptatrienyl ligand or, in some cases, at least one cycloheptatriene ligand.
- the CHT metal reactants used herein typically comprise only two ligands, one of which is a CHT ligand (cycloheptatrienyl or cycloheptatriene).
- the reactants comprise either two CHT ligands or one CHT ligand and one cyclopentadienyl (Cp) ligand.
- the CHT reactant comprises two cycloheptatrienyl ligands.
- the CHT reactant comprises two C 7 H 8 cycloheptatriene ligands.
- the CHT metal reactants comprise one CHT ligand and another ligand such as a mono or bidentate alkyl, cycloalkyl, alkoxy, amide or imido group.
- the CHT metal reactants comprise one CHT ligand and another ligand such as a dienyl ligand.
- the CHT metal reactant comprises a transition metal.
- the CHT metal reactants typically comprise one or more Group IVB metals.
- the CHT reactants do not comprise a halide.
- CHT metal reactants have the general formula:
- CHT metal reactants have the general formula:
- the CHT metal reactants have the general formula:
- the CHT metal reactants have the general formula:
- a CHT metal reactant is selected from the group consisting of reactants of the formula:
- a CHT metal reactant is selected from the group consisting of reactants of the formula:
- a CHT metal reactant can take different forms depending on the conditions.
- a CHT metal reactant may have formula (V) under some conditions, but may be in the form of formula (VI) under other conditions.
- the compound in the formulas (I)-(VI) CHT, CHD or X, denote the structure of ligand i.e. C 7 ring structure with double bonds or delocalized electrons, where different groups R 1 -R 16 can attach.
- the compound can be C 7 H 7 -M-L or ((CH 3 ) 3 C 7 H 4 )-M-L, not H 7 C 7 H 7 -M-L or (H 4 (CH 3 ) 3 C 7 H 7 )-M-L, respectively.
- one or more of the alkyl groups in R 1 -R 16 mentioned in formulas (I)-(VI) may be C 1 -C 2 alkyls, such as Me or Et, while in other embodiments one or more of the alkyl groups in R 1 -R 16 mentioned in formulas (I)-(VI) may be C 3 -C 10 alkyls, such as Pr, i Pr, Bu and t Bu.
- one or more of the R 1 -R 14 substituents mentioned in formulas (I)-(VI) are other than hydrogen. In yet other embodiments two or more of the R 1 -R 14 substituents mentioned in formulas (I)-(VI) are other than hydrogen. In yet other embodiments three or more of the R 1 -R 16 substituents mentioned in formulas (I)-(VI) are other than hydrogen.
- FIG. 1 illustrates the structures of two exemplary reactants, CpTiCHT and (MeCp)ZrCHT.
- ALD processes are generally based on controlled, self-limiting surface reactions of precursor chemicals. Gas phase reactions are avoided by feeding the precursors alternately and sequentially into the reaction chamber. Vapor phase reactants are separated from each other in the reaction chamber, for example, by removing excess reactants and/or reactant byproducts from the reaction chamber between reactant pulses.
- a substrate is loaded into a reaction chamber and is heated to a suitable deposition temperature, generally at lowered pressure.
- Deposition temperatures are typically maintained below the thermal decomposition temperature of the reactants but at a high enough level to avoid condensation of reactants and to provide the activation energy for the desired surface reactions.
- some minor decomposition may take place without significantly disrupting the step coverage and uniformity of the ALD process.
- the appropriate temperature window for any given ALD reaction will depend upon a variety of factors, including without limitation the surface termination and the particular reactant species involved.
- thin films are deposited at deposition temperatures of about 100 to about 500° C., more preferably about 150 to about 400° C. and in some embodiments about 300 to about 400° C. Particular deposition temperatures for some specific embodiments are provided below.
- metal oxide films are deposited on a substrate by atomic layer deposition (ALD) type processes utilizing one or more metalorganic precursors at temperatures greater than about 300° C. or at temperatures greater than about 350° C.
- the metalorganic precursors are organometallic precursors.
- the precursors are metal CHT precursors as described herein.
- a first transition metal reactant is conducted or pulsed into the chamber in the form of vapor phase pulse and contacted with the surface of the substrate. Conditions are preferably selected such that no more than about one monolayer of the first reactant is adsorbed on the substrate surface in a self-limiting manner. Excess first reactant and reaction byproducts, if any, are removed from the reaction chamber, such as by purging with an inert gas. The appropriate pulsing and purging times can be readily determined by the skilled artisan based on the particular circumstances.
- Purging the reaction chamber means that vapor phase precursors and/or vapor phase byproducts are removed from the reaction chamber such as by evacuating the chamber with a vacuum pump and/or by replacing the gas inside the reactor with an inert gas such as argon or nitrogen.
- Typical purging times are from about 0.05 to 20 seconds, more preferably between about 0.5 and 10, and still more preferably between about 1 and 5 seconds.
- other purge times can be utilized if necessary, such as where highly conformal step coverage over extremely high aspect ratio structures or other structures with complex surface morphology is needed.
- batch ALD reactors can utilize longer purging times because of increased volume and surface area.
- a second gaseous reactant is pulsed into the chamber where it reacts with the first reactant bound to the surface. Excess second reactant and gaseous byproducts of the surface reaction are removed from the reaction chamber, preferably by purging with the aid of an inert gas and/or evacuation. The steps of pulsing and purging are repeated until a thin film of the desired thickness has been formed on the substrate, with each cycle leaving typically less than or no more than a molecular monolayer.
- the second reactant may be, for example, an oxygen containing reactant, such that a metal oxide is formed. In other embodiments the second reactant may comprise nitrogen or carbon, in order to form metal nitrides or metal carbides, respectively.
- each pulse or phase of each cycle is preferably self-limiting.
- An excess of reactants is supplied in each phase to saturate the susceptible structure surfaces.
- Surface saturation ensures reactant occupation of all available reactive sites (subject, for example, to physical size or “steric hindrance” restraints) and thus ensures excellent step coverage.
- some minor non-self-limiting deposition may occur which does not significantly disturb the unique properties of ALD process.
- a transition metal oxide thin film preferably a Group IVB metal oxide thin film, is formed on a substrate by an ALD type process comprising multiple metal oxide deposition cycles, each metal oxide deposition cycle comprising:
- a first vapor phase reactant pulse comprising a first metalorganic reactant to the reaction chamber such that it forms no more than a monolayer on the substrate
- the metalorganic reactant comprises a transition metal, preferably a Group IVB metal;
- a second vapor phase reactant pulse comprising a second reactant to the reaction chamber, wherein the second reactant comprises oxygen; and removing excess second reactant and any reaction byproducts from the reaction chamber.
- the providing and removing steps are repeated until a thin film of a desired thickness and composition is obtained.
- the deposition cycle is carried out at a temperature of at least 300° C. or even at least 350° C.
- the metalorganic reactant is an organometallic reactant.
- the same metalorganic precursor is utilized in each cycle.
- different reactants can be utilized in one or more different cycles.
- the ALD process may begin with any phase of the deposition cycle.
- a vapor phase reactant pulse comprising a Group IVB metal CHT reactant is provided to the reaction chamber where it contacts a substrate.
- the reactant is selected such that if it decomposes at the given process conditions it does not adversely affect the deposition process.
- the metal reactant comprises one or more of Ti, Hf, and Zr.
- reactants are selected from the reactants of formula's (I), (II), (III), (IV), (V) and (VI).
- the metal CHT reactant is provided such that it forms no more than about a single molecular layer on the substrate. If necessary, any excess metal reactant can be purged or removed from the reaction space.
- the purge step can comprise stopping the flow of metal reactant while still continuing the flow of an inert carrier gas such as nitrogen or argon.
- a vapor phase reactant pulse comprising an oxygen source or precursor is provided to the substrate and reaction chamber.
- oxygen precursors can be used, including, without limitation: oxygen, plasma excited oxygen, atomic oxygen, ozone, water, nitric oxide (NO), nitrogen dioxide (NO 2 ), nitrous oxide (N 2 O), hydrogen peroxide (H 2 O 2 ), etc.
- a suitable oxygen precursor can be selected by the skilled artisan such that it reacts with the molecular layer of the metal reactant on the substrate to form a metal oxide under the particular process conditions.
- ozone is used with a metal CHT reactant.
- the oxygen source may be an oxygen-containing gas pulse and can be a mixture of an oxygen precursor and inactive gas, such as nitrogen or argon.
- the oxygen source may be a molecular oxygen-containing gas pulse.
- One source of oxygen may be air.
- the oxygen source or precursor is water.
- the oxygen source comprises an activated or excited oxygen species.
- the oxygen source comprises ozone.
- the oxygen source may be pure ozone or a mixture of ozone and another gas, for example an inactive gas such as nitrogen or argon.
- the oxygen source is oxygen plasma.
- the oxygen precursor pulse may be provided, for example, by pulsing ozone or a mixture of ozone and another gas into the reaction chamber.
- ozone or other oxygen precursor
- ozone is formed inside the reactor, for example by conducting oxygen containing gas through an arc.
- an oxygen containing plasma is formed in the reactor.
- the plasma may be formed in situ on top of the substrate or in close proximity to the substrate.
- the plasma is formed upstream of the reaction chamber in a remote plasma generator and plasma products are directed to the reaction chamber to contact the substrate.
- the pathway to the substrate can be optimized to maximize electrically neutral species and minimize ion survival before reaching the substrate.
- each metal oxide deposition cycle typically forms no more than about one molecular layer of metal oxide. If necessary, any excess reaction byproducts or oxygen precursor can be removed from the reaction space.
- the purge step can comprise stopping the flow of oxygen precursor while still continuing the flow of an inert carrier gas such as nitrogen or argon.
- the oxygen precursor has a decomposition temperature above the substrate temperature during deposition. In some embodiments the oxygen precursor may decompose at the substrate deposition temperature but does not disrupt the self limiting nature of the ALD process.
- the metal oxide deposition cycle is typically repeated a predetermined number of times 150 to form a metal oxide of the desired thickness and composition.
- multiple molecular layers of metal oxide are formed by multiple deposition cycles.
- a molecular layer or less of metal oxide is formed.
- Removing excess reactants can include evacuating some of the contents of the reaction space or purging the reaction space with argon, helium, nitrogen or any other inert gas.
- purging can comprise turning off the flow of the reactive gas while continuing to flow an inert carrier gas to the reaction space.
- the precursors employed in the ALD type processes may be solid, liquid or gaseous material under standard conditions (room temperature and atmospheric pressure), provided that the precursors are in vapor phase before it is conducted into the reaction chamber and contacted with the substrate surface.
- “Pulsing” a vaporized precursor onto the substrate means that the precursor vapor is conducted into the chamber for a limited period of time. Typically, the pulsing time is from about 0.05 to 10 seconds. However, depending on the substrate type and its surface area, the pulsing time may be even higher than 10 seconds.
- a metal precursor such as a Ti, Hf, or Zr precursor
- a metal precursor is pulsed for from 0.05 to 20 seconds, more preferably for from 0.1 to 10 seconds and most preferably for about 0.3 to 5.0 seconds.
- An oxygen-containing precursor is preferably pulsed for from about 0.05 to 10 seconds, more preferably for from 0.1 to 5 seconds, most preferably for from about 0.2 to 3.0 seconds.
- pulsing times can be on the order of minutes in some cases, for example, if the process is applied to reactors having large surface area, such batch ALD reactors. The optimum pulsing time can be readily determined by the skilled artisan based on the particular circumstances.
- the mass flow rate of the precursors can also be determined by the skilled artisan.
- the flow rate of metal precursors is preferably between about 1 and 1000 sccm without limitation, more preferably between about 100 and 500 sccm.
- the mass flow rate of the metal precursors is usually lower than the mass flow rate of the oxygen source, which is usually between about 10 and 10000 sccm without limitation, more preferably between about 100-2000 sccm and most preferably between 100-1000 sccm.
- the pressure in the reaction chamber is typically from about 0.01 to about 20 mbar, more preferably from about 1 to about 10 mbar. However, in some cases the pressure will be higher or lower than this range, as can be readily determined by the skilled artisan. Atmospheric pressure could also be used for these high temperature reactions.
- the substrate Before starting the deposition of the film, the substrate is typically heated to a suitable growth temperature. Growth temperatures are described above and typically range from about 100 to about 400° C. In some embodiments growth temperatures of greater than 300° C. or even 350° C. are used.
- the deposition cycles can be repeated a predetermined number of times or until a desired thickness is reached.
- the thin films are between about 5 ⁇ and 200 nm thick, more preferably between about 10 ⁇ and 100 nm thick.
- transition metal nitride thin films are deposited using a transition metal CHT reactant, preferably a Group IVB metal CHT reactant.
- the reaction conditions can be essentially as described above for deposition of transition metal oxide, except that a nitrogen-containing reactant is used in place of the oxygen reactant.
- Nitrogen containing reactants may be, for example, NH 3 , nitrogen plasma, N 2 H 2 , hydrogen azide, hydrazine and/or hydrazine derivatives, amines, nitrogen radicals, and other excited species of nitrogen.
- transition metal carbide thin films are deposited using a transition metal CHT reactant, preferably a Group IVB metal CHT reactant.
- a transition metal CHT reactant preferably a Group IVB metal CHT reactant.
- the reaction conditions can be essentially as described above for deposition of transition metal oxides, except that a carbon-containing reactant is used in place of the oxygen reactant.
- the carbon source is a hydrocarbon such as an alkane, alkene, and/or alkyne.
- a vapor phase pulse of a zirconium CHT precursor is provided to the reaction chamber.
- the zirconium precursor may be selected from the group consisting of the compounds of formulas (I), (II), (III), (IV), (V) and (VI) above, where M is Zr.
- the precursor is (MeCp)ZrCHT.
- the zirconium precursor can be provided such that it forms no more than one monolayer of material on the substrate.
- a vapor phase reactant pulse comprising an oxygen precursor is provided to the reaction chamber.
- the oxygen precursor can be provided such that it reacts with the zirconium precursor on the substrate surface.
- Preferred oxygen precursors include atomic oxygen, oxygen plasma, O 2 , H 2 O, O 3 , NO, NO 2 , N 2 O, and H 2 O 2 .
- the oxygen precursor is O 3 .
- the substrate temperature during pulses of zirconium and oxygen precursors is above about 300° C.
- the cycle can be generally referred to as a zirconium oxide deposition cycle. The deposition cycle can be repeated until the thin film reaches the desired thickness.
- the process conditions for the zirconium oxide deposition can be essentially as described above in reference to the metal oxide deposition cycle.
- a vapor phase pulse of a titanium CHT precursor is provided to the reaction chamber.
- the titanium precursor may be selected from the group consisting of the compounds of formulas (I), (II), (III), (IV), (V) and (VI) above, where M is Ti.
- the precursor is CpTiCHT.
- the titanium precursor can be provided such that it forms no more than one monolayer of material on the substrate.
- a vapor phase reactant pulse comprising an oxygen precursor is provided to the reaction chamber.
- the oxygen precursor can be provided such that it reacts with the titanium precursor on the substrate surface.
- Preferred oxygen precursors include atomic oxygen, oxygen plasma, O 2 , H 2 O, O 3 , NO, NO 2 , N 2 O, and H 2 O 2 .
- the oxygen precursor is O 3 .
- the substrate temperature during pulses of titanium and oxygen precursors is above about 300° C.
- the cycle can be generally referred to as a titanium oxide deposition cycle. The deposition cycle can be repeated until the thin film reaches the desired thickness.
- the process conditions for the titanium oxide deposition can be essentially as described above in reference to the metal oxide deposition cycle.
- a vapor phase pulse of a hafnium CHT precursor is provided to the reaction chamber.
- the hafnium precursor may be selected from the group consisting of the compounds of formulas (I), (II), (III), (IV), (V) and (VI) above, where M is Hf.
- the hafnium precursor can be provided such that it forms no more than one monolayer of material on the substrate.
- a vapor phase reactant pulse comprising an oxygen precursor is provided to the reaction chamber.
- the oxygen precursor can be provided such that it reacts with the hafnium precursor on the substrate surface.
- Preferred oxygen precursors include atomic oxygen, oxygen plasma, O 2z H 2 O, O 3 , NO, NO 2 , N 2 O, and H 2 O 2 .
- the oxygen precursor is O 3 .
- the substrate temperature during pulses of hafnium and oxygen precursors is above about 300° C.
- the cycle can be generally referred to as a hafnium oxide deposition cycle. The deposition cycle can be repeated until the thin film reaches the desired thickness.
- the process conditions for the hafnium oxide deposition can be essentially as described above in reference to the metal oxide deposition cycle.
- Metal oxide films may be used, for example, as dielectric layers between top and bottom electrodes in capacitors.
- a capacitor suitable for use in an integrated circuit is formed by a method comprising:
- the metal oxides can also be used as dielectric layers in transistors.
- a dielectric oxide layer is first deposited over one or more gate electrodes on a substrate by an ALD process.
- the deposition of the dielectric oxide layer can include any of the methods described herein.
- the dielectric oxide layer comprises one or more of hafnium, zirconium, and titanium.
- a semiconductor is deposited on the dielectric oxide layer.
- the semiconductor comprises one or more of silicon and germanium.
- electrically conductive source and drain electrodes are deposited on top of the semiconductor such that the drain electrodes align with the gate electrodes.
- metal oxide thin films described herein have many other uses, such as a floating gate dielectric layer in a flash device, as a blocking oxide in charge trapping flash devices, as a gate dielectric in memory stacks, as a dielectric oxide in other semiconductor devices, etc.
- the thin films described herein can also be useful in optical areas, for example, titanium dioxide can be a transparent conducting oxide used in optical components, flat panel displays, LEDs, solar cells and chemical sensors.
- CHT precursors of formulas (I), (II), (III), (IV), (V) and (VI) above can be synthesized.
- the CHT precursor that is synthesized is CpTiCHT and in other embodiments the precursor (MeCp)ZrCHT is synthesized, as described in the Examples below.
- transition metal precursors of formula (III) are synthesized, such as (C 7 H 8 )M(C 7 H 8 ), where M is a transition metal, preferably a group IVB metal such as Ti, Zr, Hf.
- M is a transition metal, preferably a group IVB metal such as Ti, Zr, Hf.
- anhydrous FeCl 3 , cycloheptatriene, and tetrahydrofuran (THF) are combined.
- a transition metal precursor, such as a transition metal halide THF adduct is added to the reaction mixture, preferably over a long period of time and while stirring. The reaction is exothermic thus, for example, the transition metal precursor may be added over a 1-h period to avoid possible overheating of the stirred reaction mixture.
- the transition metal precursor comprises a Group IVB metal in some embodiments, and may be, for example, a transition metal chloride.
- the transition metal precursor may be in solution, such as in solution with THF.
- the mixture may be stirred over night, for example at room temperature. Following stirring, the volatile products may be evaporated under vacuum.
- FIG. 1 shows the structure of CpTiCHT and FIG. 2 provides the TGA curve measured for CpTiCHT.
- FIG. 1 shows the structure of (MeCp)ZrCHT and FIG. 2 provides the TGA curve measured for this compound.
- (MeCp)ZrCHT is a solid precursor at 100° C.
- Example 1 The thermal stability of the CpTiCHT synthesized in Example 1 was tested on an extremely high surface area silica substrate and found to be good. The compound saturated the silica surface at 400° C., although the ligands are most likely decomposed. CpTiCHT was observed to be a blue solid that vaporized at 130° C.
- (MeCp)ZrCHT was synthesized as described above.
- (MeCp)ZrCHT was used in combination with O 3 in an ALD process essentially as described herein.
- An ozone concentration of 100 g/m 3 was used. Smooth, uniform zirconium oxide films were deposited at temperatures up to about 450° C. Saturation was confirmed at 350° C., and at 400° C. only slight decomposition was observed as the growth rate increased from 0.7 ⁇ /cycle with 1 s pulses of the metal precursor to 0.8 ⁇ /cycle with 2 s pulses.
- FIG. 3 According to ERDA, the films deposited at 350° C. were exceptionally pure (no H detected, ⁇ 0.06 at. % C).
- FIG. 4 the films deposited at 350° C. were exceptionally pure (no H detected, ⁇ 0.06 at. % C).
- FIGS. 5 a , 5 b and 5 c GIXRD data is presented in FIG. 6 . Similar characteristics were observed as with films deposited from (CpMe) 2 Zr(OMe)Me and O 3 .
- ZrO 2 is deposited by ALD from alternating pulses of (MeCp)ZrCHT or another CHT metal precursor and an oxygen source, such as O 3
- the substrate temperature is above 300° C.
- HfO 2 is deposited on a substrate by ALD using alternating pulses of a Hf CHT precursor and an oxygen source, such as O 3 at a substrate temperature of above 300° C.
- TiO 2 is deposited on a substrate by ALD using alternating pulses of CpTiCHT and O 3 at a substrate temperature of above 300° C.
- the chemical structure of the synthesized CHT compound was determined to be (C 7 H 7 )Ti(C 7 H 9 )/Ti(C 7 H 8 ) 2 . While this is believed to be accurate, identification of the structure was difficult and it was initially identified differently. Crystal structure of the synthesized precursors is shown in FIG. 9 . TG, DTG and SDTA curves measured for (CHT)Ti(CHD) are shown in FIG. 10 .
- transition metals precursors of formula (III), such as (C 7 H 7 )M(C 7 H 9 )/M(C 7 H 8 ) 2 , where M is a transition metal, preferably group IVB metal such as Ti, Zr, Hf, can be synthesized using essentially the method described above for synthesis of (C 7 H 7 )Ti(C 7 H 9 )/M(C 7 H 8 ) 2 .
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Abstract
Methods are provided herein for forming transition metal oxide thin films, preferably Group IVB metal oxide thin films, by atomic layer deposition. The metal oxide thin films can be deposited at high temperatures using metalorganic reactants. Metalorganic reactants comprising two ligands, at least one of which is a cycloheptatriene or cycloheptatrienyl (CHT) ligand are used in some embodiments. The metal oxide thin films can be used, for example, as dielectric oxides in transistors, flash devices, capacitors, integrated circuits, and other semiconductor applications.
Description
- The present application claims priority to U.S. provisional application No. 61/308,263, filed Feb. 25, 2010. The priority application is hereby incorporated by reference in its entirety.
- The invention claimed herein was made by, or on behalf of, and/or in connection with a joint research agreement between the University of Helsinki and ASM Microchemistry Oy signed on Nov. 14, 2003 and renewed in 2008. The agreement was in effect on and before the date the claimed invention was made, and the claimed invention was made as a result of activities undertaken within the scope of the agreement.
- 1. Field of the Invention
- The present application relates generally to methods and compositions for depositing transition metal oxide thin films, such as titanium, zirconium and hafnium oxide thin films, by atomic layer deposition using metalorganic precursors. The metalorganic precursors comprise at least one cycloheptatriene (CHT) ligand.
- 2. Description of the Related Art
- Atomic layer deposition (ALD) is a self-limiting process, whereby alternated pulses of reactants saturate a substrate surface. The deposition conditions and precursors are selected such that an adsorbed layer of precursor in one pulse leaves a surface termination that is non-reactive with the gas phase reactants of the same pulse. A subsequent pulse of different reactants reacts with the previous termination to enable continued deposition. Thus, each cycle of alternated pulses typically leaves no more than about one molecular layer of the desired material. The principles of ALD type processes have been presented by T. Suntola, e.g. in the Handbook of Crystal
Growth 3, Thin Films and Epitaxy, Part B: Growth Mechanisms and Dynamics, Chapter 14, Atomic Layer Epitaxy, pp. 601-663, Elsevier Science B.V. 1994, the disclosure of which is incorporated herein by reference. Variations of ALD have been proposed that allow for modulation of the growth rate. However, to provide for high conformality and thickness uniformity, these reactions are still more or less self-saturating. - While ALD processes can be used to deposit films at lower temperatures, typically CVD processes have been used for higher temperature growth because the reactions occur more rapidly at higher temperatures. In addition, some ALD processes can lose their self limiting nature at high temperatures. In some cases, higher temperatures can cause undesirable decomposition of some precursors. Some precursor decomposition can disrupt the self limiting nature of the ALD process, for example if the products of the decomposition reaction react with each other and/or react with the adsorbed species to deposit material on the substrate surface.
- Atomic layer deposition (ALD) of Group IVB metal oxides, such as TiOx, ZrO2 and HfO2, has been studied for years. However, higher temperature ALD options for these metal oxides are quite limited. Metal halide reactants are typically used; however, metal halides are incompatible with some materials and processes. Some metal-organic precursors have also been used. However, these reactants have not been well suited for higher temperature deposition processes.
- In accordance with one aspect of the present invention, methods for forming transition metal oxide thin films on a substrate in a reaction chamber by atomic layer deposition using metalorganic reactants are provided. Organometallic reactants are used in some embodiments. In some embodiments the transition metal oxide thin films are Group IVB metal oxide thin films. In some embodiments, the methods comprise providing a vapor phase pulse of a first reactant comprising a first Group IVB metalorganic precursor to a reaction chamber such that it forms no more than a monolayer on a substrate in the reaction chamber; removing excess first reactant from the reaction chamber; providing a vapor phase pulse of a second reactant comprising oxygen to the reaction chamber such that it converts the adsorbed Group IVB metal reactant to a metal oxide; and removing excess second reactant and any reaction byproducts from the reaction chamber. The providing and removing steps are repeated until a thin metal oxide film of a desired thickness and composition is obtained. The substrate temperature during the providing and removing steps may be above about 300° C., more preferably above about 350° C. In some embodiments the metalorganic precursor is an organometallic precursor, comprising a carbon-metal bond.
- In accordance with another aspect of the present invention, methods for forming transition metal oxide films, preferably Group IVB metal oxide films, by atomic layer deposition comprise alternately and sequentially contacting a substrate with vapor phase pulses of a cycloheptatrienyl or cycloheptatriene (CHT) metal reactant and an oxygen source. The alternate and sequential pulses are repeated until a thin film of a desired thickness is obtained.
- CHT metal reactants are metalorganic, typically organometallic compounds, comprising at least one chycloheptatrienyl or cycloheptatriene ligand (a CHT ligand). In some embodiments the CHT metal reactant comprises only two ligands, including at least one cycloheptatrienyl or cycloheptatriene (CHT) ligand. In some embodiments the CHT metal reactant comprises two CHT ligands. In some embodiments the CHT metal reactant comprises two cycloheptatrienyl ligands. In other embodiments the CHT metal reactant comprises one CHT ligand and one cyclopentadienyl ligand (Cp). In some embodiments, the CHT reactant does not comprise a halide. In some embodiments, the CHT reactant comprises one cycloheptadienyl (CHD) ligand. In some embodiments, the CHT reactant comprises two C7H8 cycloheptatriene ligands.
- In some embodiments, a CHT metal reactant is selected from the group consisting of reactants of the formula:
-
- (I) RxCp-M-CHT, where RxCp represents substituted or unsubstituted cyclopentadienyl, CHT is cycloheptatrienyl (C7H7) and M is selected from Ti, Zr and Hf.
- In other embodiments, a CHT metal reactant is selected from the group consisting of reactants of the formula:
-
- (II) (R1R2R3R4R5R6R7)CHT-M-Cp(R8R9R10R11R12), where M is selected from Ti, Zr and Hf, R1-12 can independently be H or an alkyl group.
- In other embodiments, a CHT metal reactant is selected from the group consisting of reactants of the formula:
-
- (III) (R1R2R3R4R5R6R7)CHT-M-CHT(R8R9R10R11R12R13R14), where M is selected from Ti, Zr and Hf, R1-14 can independently be H or an alkyl group.
- In other embodiments, a CHT metal reactant is selected from the group consisting of reactants of the formula:
-
- (IV) (R1R2R3R4R5R6R7)CHT-M-L, where M is selected from Ti, Zr and Hf, R1-7 can independently be H or an alkyl group and L is a mono or bidentate alkyl, cycloalkyl, alkoxy, amide or imido group. L may also be a acyclic or cyclic dienyl ligand.
- In other embodiments, a CHT metal reactant is selected from the group consisting of reactants of the formula:
-
- (V) (R1R2R3R4R5R6R7)CHT-M-CHD(R8R9R10R11R12R13R14R15R16), where M is selected from Ti, Zr and Hf, R1-16 can independently be H or an alkyl group and CHD is a cyloheptadienyl (C7H9).
- In other embodiments a CHT reactant it is selected from the group consisting of reactants of the formula:
-
- (VI) (R1R2R3R4R5R6R7R8)X-M-X(R9R10R11R12R13R14R15R16), where M is selected from Ti, Zr and Hf, R1-14 can independently be H or an alkyl group and X is cycloheptariene (C7H8).
- In some embodiments, a CHT metal reactant can take different forms depending on the conditions. For example, in some embodiments a CHT metal reactant may have formula (V) under some conditions, but may be in the form of formula (VI) under other conditions.
- In the formulas (I)-(VI) CHT, CHD or X, denote the structure of the ligand i.e. C7 ring structure with double bonds or delocalized electrons, where different groups R1-R16 can attach. For example, according to formula (IV) the compound can be C7H7-M-L or ((CH3)3C7H4)-M-L, not H7C7H7-M-L or (H4(CH3)3C7H7)-M-L, respectively.
- In another aspect of the invention, transition metal nitride thin films, such as Group IVB metal nitride films, are deposited by ALD using a transition metal CHT reactant and a nitrogen containing reactant. In some embodiments the metal CHT reactant comprises two CHT ligands. In some embodiments the CHT reactant does not comprise a Cp group. In some embodiments, the CHT reactant comprises two C7H8 cycloheptatriene ligands.
- In still another aspect of the invention, transition metal carbide thin films, such as Group IVB metal carbide films, are deposited by ALD using a metal CHT reactant. In some embodiments the metal CHT reactant comprises two CHT ligands. In some embodiments, the CHT reactant does comprise two C7H8 cycloheptatriene ligands.
- In another aspect of the invention, methods of synthesizing transition metal precursors comprising one or more CHT ligands are provided. In some embodiments, methods of synthesizing (C7H8)M(C7H8), where M is a transition metal, preferably a Group IVB metal, are provided. The methods may comprise forming a reaction mixture by combining a transition metal reactant with ferric chloride, cycloheptatriene and tetrahydrofuran (THF) in a flask containing magnesium chips. The transition metal reactant may be, for example, a Group IVB transition metal reactant, preferably a metal halide. Exemplary reactants include transition metal chlorides. In one embodiment, the transition metal reactant is TiCl4.
- These and other embodiments will become readily apparent to those skilled in the art from the following detailed description, the invention not being limited to any particular preferred embodiments disclosed.
- Certain objects and advantages of the disclosed precursors and methods have been described herein. Of course, it is to be understood that not necessarily all such objects or advantages may be achieved in accordance with any particular embodiment. Thus, for example, those skilled in the art will recognize that the invention may be embodied or carried out in a manner that achieves or optimizes one advantage or group of advantages as taught herein without necessarily achieving other objects or advantages.
-
FIG. 1 shows the structure of CpTiCHT (left) and (MeCp)ZrCHT (right). -
FIG. 2 shows the TGA curves measured for CpTiCHT and (MeCp)ZrCHT. -
FIG. 3 is a graph of growth rate at various temperatures (top) and a graph of saturation as measured by growth rate for different metal reactant pulse lengths (bottom). -
FIG. 4 shows TofERDA data for ZrO2 films deposited using (MeCp)ZrCHT and O3 at various temperatures. -
FIGS. 5 a, 5 b and 5c show XRD data for ZrO2 films deposited using (MeCp)ZrCHT and O3 at various temperatures. -
FIG. 6 represents graphs of GIXRD data for ZrO2 films deposited using (MeCp)ZrCHT and O3. -
FIG. 7 illustrates experiments to characterize the electrical properties of ZrO2 films deposited using (MeCp)ZrCHT and O3. -
FIG. 8 is a flow chart of an embodiment of an ALD process for depositing a Group IVB metal oxide using a CHT metal precursor. -
FIG. 9 is a schematic of the crystal structure of Ti(C7H8)2. The formulation may also be (C7H7)Ti(C7H9) i.e. (CHT)Ti(CHD). -
FIG. 10 shows TG, DTG and SDTA curves measured for (CHT)Ti(CHD). - Methods and compositions for forming transition metal oxide films using metalorganic precursors are described herein. While primarily illustrated in the context of forming Group IVB metal oxide films, other transition metals can be substituted for the Group IVB metals in some embodiments, as will be recognized by the skilled artisan. In addition, although the thin films are generally described with respect to the formation of an integrated circuit, such as a capacitor or transistor, the skilled artisan will readily appreciate the application of the principles and advantages disclosed herein to various contexts in which metal oxide thin films are useful. For example, transparent titanium oxide films can be used in flat panel displays, LEDs, and solar cells.
- In addition, although illustrated primarily in terms of deposition of transition metal oxide thin films, in some embodiments transition metal nitride or metal carbide films, such as Group IVB metal nitride and carbide films, can be deposited by ALD using the disclosed metal precursors.
- As used herein, the term metal oxide film refers to a transition metal oxide film unless otherwise stated. Preferred transition metal oxide films are Group IVB metal oxide films. Group IVB metal oxide thin films include oxide films comprising titanium (Ti), zirconium (Zr) and/or hafnium (Hf). Exemplary Group IVB metal oxide films that are specifically discussed herein include TiO2, ZrO2 and HfO2. Other Group IVB metal oxide films will be apparent to the skilled artisan. In addition, as noted above, in some embodiments the Group IVB metals can be substituted with other transition metals, as will be understood by the skilled artisan.
- In some embodiments, transition metal oxide films are deposited on a substrate by atomic layer deposition (ALD) type processes utilizing one or more metalorganic precursors. In some embodiments the metalorganic precursor is an organometallic precursor and thus comprises a carbon-metal bond. As discussed below, in some embodiments deposition temperatures of greater than 300° C. are used. In other embodiments, deposition temperatures of greater than 350° C. are used.
- In particular embodiments, CHT metal reactants are utilized. CHT metal reactants are metal reactants comprising at least one CHT ligand. The CHT metal reactant may be a metalorganic compound and in some embodiments is an organometallic compound. CHT ligands are cycloheptatrienyl and cycloheptatriene ligands. Thus, CHT metal reactants comprise at least one cycloheptatrienyl ligand or, in some cases, at least one cycloheptatriene ligand. The CHT metal reactants used herein typically comprise only two ligands, one of which is a CHT ligand (cycloheptatrienyl or cycloheptatriene). In some embodiments, the reactants comprise either two CHT ligands or one CHT ligand and one cyclopentadienyl (Cp) ligand. In some embodiments the CHT reactant comprises two cycloheptatrienyl ligands. In some embodiments, the CHT reactant comprises two C7H8 cycloheptatriene ligands. In other embodiments the CHT metal reactants comprise one CHT ligand and another ligand such as a mono or bidentate alkyl, cycloalkyl, alkoxy, amide or imido group. In other embodiments the CHT metal reactants comprise one CHT ligand and another ligand such as a dienyl ligand. In some embodiments the CHT metal reactant comprises a transition metal. However, the CHT metal reactants typically comprise one or more Group IVB metals. In some embodiments, the CHT reactants do not comprise a halide.
- In some embodiments, CHT metal reactants have the general formula:
-
- (I) RxCp-M-CHT, where RxCp represents substituted or unsubstituted cyclopentadienyl, CHT is cycloheptatrienyl (C7H7) and M is selected from Ti, Zr and Hf.
- In other embodiments, CHT metal reactants have the general formula:
-
- (II) (R1R2R3R4R5R6R7)CHT-M-Cp(R8R9R10R11R12), where M is selected from Ti, Zr and Hf, R1-12 can independently be H or an alkyl group, and may be a bridged or substituted alkyl. Exemplary alkyl groups include, but are not limited to Me, Et, Pr, iPr, Bu, tBu and other C1-C10 alkyls. Other alkyl groups that may be used will be apparent to the skilled artisan.
- In still other embodiments, the CHT metal reactants have the general formula:
-
- (III) (R1R2R3R4R5R6R7)CHT-M-CHT(R8R9R10R11R12R13R14), where M is selected from Ti, Zr and Hf, R1-14 can independently be H or an alkyl group, and may be a bridged or substituted alkyl. Exemplary alkyl groups include, but are not limited to Me, Et, Pr, iPr, Bu, tBu and other C1-C10 alkyls. Other alkyl groups that may be used will be apparent to the skilled artisan.
- In still other embodiments, the CHT metal reactants have the general formula:
-
- (IV) (R1R2R3R4R5R6R7)CHT-M-L, where M is selected from Ti, Zr and Hf; R1-7 can independently be H or an alkyl group, and may be a bridged or substituted alkyl; and L is either a mono or bidentate alkyl, cycloalkyl, alkoxy, amide or imido group. L may also be a acyclic or cyclic dienyl ligand. Exemplary alkyl groups include, but are not limited to Me, Et, Pr, iPr, Bu, tBu and other C1-C10 alkyls. Other alkyl groups that may be used will be apparent to the skilled artisan. Exemplary alkoxy groups include OMe, OEt, OiPr, OtBu, O2CMe and O2CtBu. Exemplary amide groups include N(Me)2, N(MeEt) and N(Et)2. Exemplary dienyl ligands include 2,4-dimethylpenta-1,4-dienyl and hepta-2,5-dienyl.
- In other embodiments, a CHT metal reactant is selected from the group consisting of reactants of the formula:
-
- (V) (R1R2R3R4R5R6R7)CHT-M-CHD(R8R9R10R11R12R13R14R15R16), where M is selected from Ti, Zr and Hf; R1-16 can independently be H or an alkyl group, and may be a bridged or substituted alkyl. Exemplary alkyl groups include, but are not limited to Me, Et, Pr, iPr, Bu, tBu and other C1-C10 alkyls. Other alkyl groups that may be used will be apparent to the skilled artisan. CHD is a cyloheptadiene (C7H9).
- In other embodiments, a CHT metal reactant is selected from the group consisting of reactants of the formula:
-
- (VI) (R1R2R3R4R5R6R7R8)X-M-X(R9R10R11R12R13R14R15R16), where M is selected from Ti, Zr and Hf; R1-16 can independently be H or an alkyl group, and may be a bridged or substituted alkyl. Exemplary alkyl groups include, but are not limited to Me, Et, Pr, iPr, Bu, tBu and other C1-C10 alkyls. Other alkyl groups that may be used will be apparent to the skilled artisan. X is cycloheptatriene (C7H8).
- In some embodiments, a CHT metal reactant can take different forms depending on the conditions. For example, in some embodiments a CHT metal reactant may have formula (V) under some conditions, but may be in the form of formula (VI) under other conditions.
- In the formulas (I)-(VI) CHT, CHD or X, denote the structure of ligand i.e. C7 ring structure with double bonds or delocalized electrons, where different groups R1-R16 can attach. For example, according to formula (IV) the compound can be C7H7-M-L or ((CH3)3C7H4)-M-L, not H7C7H7-M-L or (H4(CH3)3C7H7)-M-L, respectively.
- In some embodiments one or more of the alkyl groups in R1-R16 mentioned in formulas (I)-(VI) may be C1-C2 alkyls, such as Me or Et, while in other embodiments one or more of the alkyl groups in R1-R16 mentioned in formulas (I)-(VI) may be C3-C10 alkyls, such as Pr, iPr, Bu and tBu.
- In some embodiments one or more of the R1-R14 substituents mentioned in formulas (I)-(VI) are other than hydrogen. In yet other embodiments two or more of the R1-R14 substituents mentioned in formulas (I)-(VI) are other than hydrogen. In yet other embodiments three or more of the R1-R16 substituents mentioned in formulas (I)-(VI) are other than hydrogen.
-
FIG. 1 illustrates the structures of two exemplary reactants, CpTiCHT and (MeCp)ZrCHT. - ALD processes are generally based on controlled, self-limiting surface reactions of precursor chemicals. Gas phase reactions are avoided by feeding the precursors alternately and sequentially into the reaction chamber. Vapor phase reactants are separated from each other in the reaction chamber, for example, by removing excess reactants and/or reactant byproducts from the reaction chamber between reactant pulses.
- Briefly, a substrate is loaded into a reaction chamber and is heated to a suitable deposition temperature, generally at lowered pressure. Deposition temperatures are typically maintained below the thermal decomposition temperature of the reactants but at a high enough level to avoid condensation of reactants and to provide the activation energy for the desired surface reactions. However, in some embodiments some minor decomposition may take place without significantly disrupting the step coverage and uniformity of the ALD process. Of course, the appropriate temperature window for any given ALD reaction will depend upon a variety of factors, including without limitation the surface termination and the particular reactant species involved.
- In some embodiments, thin films are deposited at deposition temperatures of about 100 to about 500° C., more preferably about 150 to about 400° C. and in some embodiments about 300 to about 400° C. Particular deposition temperatures for some specific embodiments are provided below.
- In some embodiments, metal oxide films are deposited on a substrate by atomic layer deposition (ALD) type processes utilizing one or more metalorganic precursors at temperatures greater than about 300° C. or at temperatures greater than about 350° C. In some of these embodiments, the metalorganic precursors are organometallic precursors. In some embodiments the precursors are metal CHT precursors as described herein.
- A first transition metal reactant is conducted or pulsed into the chamber in the form of vapor phase pulse and contacted with the surface of the substrate. Conditions are preferably selected such that no more than about one monolayer of the first reactant is adsorbed on the substrate surface in a self-limiting manner. Excess first reactant and reaction byproducts, if any, are removed from the reaction chamber, such as by purging with an inert gas. The appropriate pulsing and purging times can be readily determined by the skilled artisan based on the particular circumstances.
- Purging the reaction chamber means that vapor phase precursors and/or vapor phase byproducts are removed from the reaction chamber such as by evacuating the chamber with a vacuum pump and/or by replacing the gas inside the reactor with an inert gas such as argon or nitrogen. Typical purging times are from about 0.05 to 20 seconds, more preferably between about 0.5 and 10, and still more preferably between about 1 and 5 seconds. However, other purge times can be utilized if necessary, such as where highly conformal step coverage over extremely high aspect ratio structures or other structures with complex surface morphology is needed. Also, batch ALD reactors can utilize longer purging times because of increased volume and surface area.
- A second gaseous reactant is pulsed into the chamber where it reacts with the first reactant bound to the surface. Excess second reactant and gaseous byproducts of the surface reaction are removed from the reaction chamber, preferably by purging with the aid of an inert gas and/or evacuation. The steps of pulsing and purging are repeated until a thin film of the desired thickness has been formed on the substrate, with each cycle leaving typically less than or no more than a molecular monolayer. The second reactant may be, for example, an oxygen containing reactant, such that a metal oxide is formed. In other embodiments the second reactant may comprise nitrogen or carbon, in order to form metal nitrides or metal carbides, respectively.
- As mentioned above, each pulse or phase of each cycle is preferably self-limiting. An excess of reactants is supplied in each phase to saturate the susceptible structure surfaces. Surface saturation ensures reactant occupation of all available reactive sites (subject, for example, to physical size or “steric hindrance” restraints) and thus ensures excellent step coverage. However, in some embodiments, some minor non-self-limiting deposition may occur which does not significantly disturb the unique properties of ALD process.
- According to some embodiments, a transition metal oxide thin film, preferably a Group IVB metal oxide thin film, is formed on a substrate by an ALD type process comprising multiple metal oxide deposition cycles, each metal oxide deposition cycle comprising:
- providing a first vapor phase reactant pulse comprising a first metalorganic reactant to the reaction chamber such that it forms no more than a monolayer on the substrate,
- wherein the metalorganic reactant comprises a transition metal, preferably a Group IVB metal;
- removing excess first reactant from the reaction chamber;
- providing a second vapor phase reactant pulse comprising a second reactant to the reaction chamber, wherein the second reactant comprises oxygen; and removing excess second reactant and any reaction byproducts from the reaction chamber.
- The providing and removing steps are repeated until a thin film of a desired thickness and composition is obtained. In some embodiments, the deposition cycle is carried out at a temperature of at least 300° C. or even at least 350° C.
- Further, in some embodiments the metalorganic reactant is an organometallic reactant.
- In some embodiments the same metalorganic precursor is utilized in each cycle. However, in other embodiments, different reactants can be utilized in one or more different cycles. In addition, the ALD process may begin with any phase of the deposition cycle.
- In one embodiment illustrated in
FIG. 8 , a vapor phase reactant pulse comprising a Group IVB metal CHT reactant is provided to the reaction chamber where it contacts a substrate. Preferably the reactant is selected such that if it decomposes at the given process conditions it does not adversely affect the deposition process. Preferably the metal reactant comprises one or more of Ti, Hf, and Zr. In some embodiments, reactants are selected from the reactants of formula's (I), (II), (III), (IV), (V) and (VI). - Preferably, the metal CHT reactant is provided such that it forms no more than about a single molecular layer on the substrate. If necessary, any excess metal reactant can be purged or removed from the reaction space. In some embodiments, the purge step can comprise stopping the flow of metal reactant while still continuing the flow of an inert carrier gas such as nitrogen or argon.
- Next, a vapor phase reactant pulse comprising an oxygen source or precursor is provided to the substrate and reaction chamber. Any of a variety of oxygen precursors can be used, including, without limitation: oxygen, plasma excited oxygen, atomic oxygen, ozone, water, nitric oxide (NO), nitrogen dioxide (NO2), nitrous oxide (N2O), hydrogen peroxide (H2O2), etc. A suitable oxygen precursor can be selected by the skilled artisan such that it reacts with the molecular layer of the metal reactant on the substrate to form a metal oxide under the particular process conditions. In some embodiments, ozone is used with a metal CHT reactant.
- The oxygen source may be an oxygen-containing gas pulse and can be a mixture of an oxygen precursor and inactive gas, such as nitrogen or argon. In some embodiments the oxygen source may be a molecular oxygen-containing gas pulse. One source of oxygen may be air. In some embodiments, the oxygen source or precursor is water. In some embodiments the oxygen source comprises an activated or excited oxygen species. In some embodiments the oxygen source comprises ozone. The oxygen source may be pure ozone or a mixture of ozone and another gas, for example an inactive gas such as nitrogen or argon. In other embodiments the oxygen source is oxygen plasma.
- The oxygen precursor pulse may be provided, for example, by pulsing ozone or a mixture of ozone and another gas into the reaction chamber. In other embodiments, ozone (or other oxygen precursor) is formed inside the reactor, for example by conducting oxygen containing gas through an arc. In other embodiments an oxygen containing plasma is formed in the reactor. In some embodiments the plasma may be formed in situ on top of the substrate or in close proximity to the substrate. In other embodiments the plasma is formed upstream of the reaction chamber in a remote plasma generator and plasma products are directed to the reaction chamber to contact the substrate. As will be appreciated by the skilled artisan, in the case of remote plasma the pathway to the substrate can be optimized to maximize electrically neutral species and minimize ion survival before reaching the substrate.
- Each metal oxide deposition cycle typically forms no more than about one molecular layer of metal oxide. If necessary, any excess reaction byproducts or oxygen precursor can be removed from the reaction space. In some embodiments, the purge step can comprise stopping the flow of oxygen precursor while still continuing the flow of an inert carrier gas such as nitrogen or argon. Preferably the oxygen precursor has a decomposition temperature above the substrate temperature during deposition. In some embodiments the oxygen precursor may decompose at the substrate deposition temperature but does not disrupt the self limiting nature of the ALD process.
- The metal oxide deposition cycle is typically repeated a predetermined number of
times 150 to form a metal oxide of the desired thickness and composition. In some embodiments, multiple molecular layers of metal oxide are formed by multiple deposition cycles. In other embodiments, a molecular layer or less of metal oxide is formed. - Removing excess reactants can include evacuating some of the contents of the reaction space or purging the reaction space with argon, helium, nitrogen or any other inert gas. In some embodiments purging can comprise turning off the flow of the reactive gas while continuing to flow an inert carrier gas to the reaction space.
- The precursors employed in the ALD type processes may be solid, liquid or gaseous material under standard conditions (room temperature and atmospheric pressure), provided that the precursors are in vapor phase before it is conducted into the reaction chamber and contacted with the substrate surface. “Pulsing” a vaporized precursor onto the substrate means that the precursor vapor is conducted into the chamber for a limited period of time. Typically, the pulsing time is from about 0.05 to 10 seconds. However, depending on the substrate type and its surface area, the pulsing time may be even higher than 10 seconds. Preferably, for a 300 mm wafer in a single wafer ALD reactor, a metal precursor, such as a Ti, Hf, or Zr precursor, is pulsed for from 0.05 to 20 seconds, more preferably for from 0.1 to 10 seconds and most preferably for about 0.3 to 5.0 seconds. An oxygen-containing precursor is preferably pulsed for from about 0.05 to 10 seconds, more preferably for from 0.1 to 5 seconds, most preferably for from about 0.2 to 3.0 seconds. However, pulsing times can be on the order of minutes in some cases, for example, if the process is applied to reactors having large surface area, such batch ALD reactors. The optimum pulsing time can be readily determined by the skilled artisan based on the particular circumstances.
- The mass flow rate of the precursors can also be determined by the skilled artisan. In one embodiment, for deposition on 300 mm wafers the flow rate of metal precursors is preferably between about 1 and 1000 sccm without limitation, more preferably between about 100 and 500 sccm. The mass flow rate of the metal precursors is usually lower than the mass flow rate of the oxygen source, which is usually between about 10 and 10000 sccm without limitation, more preferably between about 100-2000 sccm and most preferably between 100-1000 sccm.
- The pressure in the reaction chamber is typically from about 0.01 to about 20 mbar, more preferably from about 1 to about 10 mbar. However, in some cases the pressure will be higher or lower than this range, as can be readily determined by the skilled artisan. Atmospheric pressure could also be used for these high temperature reactions.
- Before starting the deposition of the film, the substrate is typically heated to a suitable growth temperature. Growth temperatures are described above and typically range from about 100 to about 400° C. In some embodiments growth temperatures of greater than 300° C. or even 350° C. are used.
- The deposition cycles can be repeated a predetermined number of times or until a desired thickness is reached. Preferably, the thin films are between about 5 Å and 200 nm thick, more preferably between about 10 Å and 100 nm thick.
- In other embodiments, transition metal nitride thin films are deposited using a transition metal CHT reactant, preferably a Group IVB metal CHT reactant. The reaction conditions can be essentially as described above for deposition of transition metal oxide, except that a nitrogen-containing reactant is used in place of the oxygen reactant. Nitrogen containing reactants may be, for example, NH3, nitrogen plasma, N2H2, hydrogen azide, hydrazine and/or hydrazine derivatives, amines, nitrogen radicals, and other excited species of nitrogen.
- In other embodiments, transition metal carbide thin films are deposited using a transition metal CHT reactant, preferably a Group IVB metal CHT reactant. Again, the reaction conditions can be essentially as described above for deposition of transition metal oxides, except that a carbon-containing reactant is used in place of the oxygen reactant. In some embodiments, the carbon source is a hydrocarbon such as an alkane, alkene, and/or alkyne.
- In some embodiments, methods are provided for depositing thin films comprising zirconium oxide. A vapor phase pulse of a zirconium CHT precursor is provided to the reaction chamber. The zirconium precursor may be selected from the group consisting of the compounds of formulas (I), (II), (III), (IV), (V) and (VI) above, where M is Zr. In some embodiments the precursor is (MeCp)ZrCHT. The zirconium precursor can be provided such that it forms no more than one monolayer of material on the substrate. Next, a vapor phase reactant pulse comprising an oxygen precursor is provided to the reaction chamber. The oxygen precursor can be provided such that it reacts with the zirconium precursor on the substrate surface. Preferred oxygen precursors include atomic oxygen, oxygen plasma, O2, H2O, O3, NO, NO2, N2O, and H2O2. In some embodiments the oxygen precursor is O3. Preferably the substrate temperature during pulses of zirconium and oxygen precursors is above about 300° C. The cycle can be generally referred to as a zirconium oxide deposition cycle. The deposition cycle can be repeated until the thin film reaches the desired thickness.
- The process conditions for the zirconium oxide deposition can be essentially as described above in reference to the metal oxide deposition cycle.
- In some embodiments, methods are provided for depositing thin films comprising titanium oxide. A vapor phase pulse of a titanium CHT precursor is provided to the reaction chamber. The titanium precursor may be selected from the group consisting of the compounds of formulas (I), (II), (III), (IV), (V) and (VI) above, where M is Ti. In some embodiments the precursor is CpTiCHT. The titanium precursor can be provided such that it forms no more than one monolayer of material on the substrate. Next, a vapor phase reactant pulse comprising an oxygen precursor is provided to the reaction chamber. The oxygen precursor can be provided such that it reacts with the titanium precursor on the substrate surface. Preferred oxygen precursors include atomic oxygen, oxygen plasma, O2, H2O, O3, NO, NO2, N2O, and H2O2. In some embodiments the oxygen precursor is O3. Preferably the substrate temperature during pulses of titanium and oxygen precursors is above about 300° C. The cycle can be generally referred to as a titanium oxide deposition cycle. The deposition cycle can be repeated until the thin film reaches the desired thickness.
- The process conditions for the titanium oxide deposition can be essentially as described above in reference to the metal oxide deposition cycle.
- In some embodiments, methods are provided for depositing thin films comprising hafnium oxide. A vapor phase pulse of a hafnium CHT precursor is provided to the reaction chamber. The hafnium precursor may be selected from the group consisting of the compounds of formulas (I), (II), (III), (IV), (V) and (VI) above, where M is Hf. The hafnium precursor can be provided such that it forms no more than one monolayer of material on the substrate. Next, a vapor phase reactant pulse comprising an oxygen precursor is provided to the reaction chamber. The oxygen precursor can be provided such that it reacts with the hafnium precursor on the substrate surface. Preferred oxygen precursors include atomic oxygen, oxygen plasma, O2z H2O, O3, NO, NO2, N2O, and H2O2. In some embodiments the oxygen precursor is O3. Preferably the substrate temperature during pulses of hafnium and oxygen precursors is above about 300° C. The cycle can be generally referred to as a hafnium oxide deposition cycle. The deposition cycle can be repeated until the thin film reaches the desired thickness.
- The process conditions for the hafnium oxide deposition can be essentially as described above in reference to the metal oxide deposition cycle.
- Metal oxide films may be used, for example, as dielectric layers between top and bottom electrodes in capacitors. In some embodiments, a capacitor suitable for use in an integrated circuit is formed by a method comprising:
- depositing a bottom electrode;
- depositing a dielectric oxide layer over the bottom electrode by an atomic layer deposition process comprising alternating and sequential pulses of a metal CHT source and pulses of an oxygen source as described herein; and
- depositing a top electrode directly over and contacting the dielectric layer.
- The metal oxides can also be used as dielectric layers in transistors. In one embodiment of a method for forming a transistor in an integrated circuit, a dielectric oxide layer is first deposited over one or more gate electrodes on a substrate by an ALD process. The deposition of the dielectric oxide layer can include any of the methods described herein. Preferably the dielectric oxide layer comprises one or more of hafnium, zirconium, and titanium. Next, a semiconductor is deposited on the dielectric oxide layer. In some embodiments the semiconductor comprises one or more of silicon and germanium. Next, electrically conductive source and drain electrodes are deposited on top of the semiconductor such that the drain electrodes align with the gate electrodes.
- The skilled artisan will appreciate that the metal oxide thin films described herein have many other uses, such as a floating gate dielectric layer in a flash device, as a blocking oxide in charge trapping flash devices, as a gate dielectric in memory stacks, as a dielectric oxide in other semiconductor devices, etc. The thin films described herein can also be useful in optical areas, for example, titanium dioxide can be a transparent conducting oxide used in optical components, flat panel displays, LEDs, solar cells and chemical sensors.
- Methods are also provided for synthesizing the metal CHT precursors used in the ALD processes described herein. In particular, CHT precursors of formulas (I), (II), (III), (IV), (V) and (VI) above, can be synthesized.
- In some embodiments the CHT precursor that is synthesized is CpTiCHT and in other embodiments the precursor (MeCp)ZrCHT is synthesized, as described in the Examples below.
- In other embodiments, transition metal precursors of formula (III) are synthesized, such as (C7H8)M(C7H8), where M is a transition metal, preferably a group IVB metal such as Ti, Zr, Hf. In a container containing magnesium chips, anhydrous FeCl3, cycloheptatriene, and tetrahydrofuran (THF) are combined. A transition metal precursor, such as a transition metal halide THF adduct is added to the reaction mixture, preferably over a long period of time and while stirring. The reaction is exothermic thus, for example, the transition metal precursor may be added over a 1-h period to avoid possible overheating of the stirred reaction mixture. The transition metal precursor comprises a Group IVB metal in some embodiments, and may be, for example, a transition metal chloride. The transition metal precursor may be in solution, such as in solution with THF.
- The mixture may be stirred over night, for example at room temperature. Following stirring, the volatile products may be evaporated under vacuum.
- Synthesis of C7H8—Ti—C7H8 using TiCl4 is described in Example 8 below.
- All complex preparations were done under exclusion of air and moisture using standard Schlenk and glove box techniques. Toluene and xylene were dried and stored over 4 Å molecular sieves. THF was freshly distilled from sodium benzophenone ketyl. Anhydrous Zirconium(IV) chloride (Aldrich 99.999%), Titanium(IV) chloride (Fluka >99.0%), Dicyclopentadienyl Titanium(IV) dichloride (Aldrich 97%), ferric chloride (Riedel-de Haen), magnesium turnings and cycloheptariene (
Aldrich 90%) were used as received. Methylcyclopentadiene dimer was cracked to corresponding monomer just before usage. - 1H and 13C NMR spectra were recorded with a Varian Gemini 2000 instrument at ambient temperature. Chemical shifts were referenced to SiMe4 and are given in ppm. Thermogravimetric analyses were carried out on a Mettler Toledo Stare system equipped with a TGA 850 thermobalance using a flowing nitrogen atmosphere at 1 atm. The heating rate was 10° C./min and the weights of the samples prepared to 70 μl pans were between 10-11 mg. Melting points were taken from the SDTA data measured by the thermobalance. Mass spectra were recorded with a JEOL JMS-SX102 operating in electron impact mode (70 eV) using a direct insertion probe and sublimation temperature range of 50-370° C.
- Synthesis of (C5H5)Ti(C7H7): The synthesis was done using the method of Demerseman et al. (Inorg. Chem. 1982, 21, 3942). CpTiCl3 had to be synthesized initially and two different methods were employed synthesizing different batches. First the method of Sloan at al. (J. Am. Chem. Soc. 1959, 81, 1364.) was employed. The method of Hitchcock et al. (Dalton Trans., 1999, 1161.) was also used as Cp2TiCl2 is readily available.
- In a 1-L flask containing 20 g of magnesium chips were added 2 g of anhydrous FeCl3, 50 ml of cycloheptatriene, 50 ml of THF, and, over a 3-h period to allow the warming of the stirred reaction mixture, a solution of 57.45 g (0.26 mol) of CpTiCl3 in 400 ml of THF. The mixture was stirred at room temperature over night and the volatile products were evaporated under vacuum. Sublimation of the residue (130° C./0.05 mmHg) gave a blue solid: 85.8% yield (45.9 g); 1H NMR (C6D6):), 4.91 (s, 5H, CH), 5.43 (s, 7H, CH); 13C{1H} NMR(C6D6): 97.35 (CH, C7-ring), 86.71 (CH, Cp ring); MS (EI, 70 eV) m/z: 204 (M+) with the correct isotopic distribution.
-
FIG. 1 shows the structure of CpTiCHT andFIG. 2 provides the TGA curve measured for CpTiCHT. - Synthesis of (MeC5H4)Zr(C7H7): The synthesis was performed in a fashion similar to that described for CpZrCHT by Tamm et al. (Organometallics 2005, 3163). The method is also similar with that presented for CpTiCHT in Example 1 above. MeCpZrCl3 needed in the synthesis was synthesized using the method of Hitchcock et al. (Polyhedron 1995, 14, 2745). A Schlenk flask was charged with magnesium turnings (6 g, 247 mmol), catalytic amounts of ferric chloride (0.6 g, 3.7 mmol), cycloheptatriene (15 ml), and THF (50 ml). This reaction mixture was treated dropwise with a solution of MeCpZrCl3 (17.3 g, 62.4 mmol) in THF (150 ml) over a period of 1 h. After the mixture was stirred overnight at room temperature, all volatiles were removed in vacuo. The air-sensitive residue was sublimed at 140° C./0.05 mbar to obtain 13.0 g (79.6%) of (MeC5H4)Zr(C7H7) as a purple crystalline solid. Anal. calcd. for Zr1C13H14: C, 33.65; H, 6.35. Found: C, 26.963; H, 5.03. Mp. 174-176° C., 1H NMR (C6D6) 1.81 (s, 3H, CH3), 5.14 (t, 2H, CH)), 5.23 (m, 2H, CH) 5.24 (s, 7H, CH); 13C{1H} NMR (C6D6) 14.61 (CH3), 41.74 (Cp ring), 81.39 (C7-ring), 100.92 (Cp ring), 103.34 (Cp ring). MS (EI, 70 eV) m/z: 260 (M+) with the correct isotopic distribution.
-
FIG. 1 shows the structure of (MeCp)ZrCHT andFIG. 2 provides the TGA curve measured for this compound. (MeCp)ZrCHT is a solid precursor at 100° C. - The thermal stability of the CpTiCHT synthesized in Example 1 was tested on an extremely high surface area silica substrate and found to be good. The compound saturated the silica surface at 400° C., although the ligands are most likely decomposed. CpTiCHT was observed to be a blue solid that vaporized at 130° C.
- (MeCp)ZrCHT was synthesized as described above. (MeCp)ZrCHT was used in combination with O3 in an ALD process essentially as described herein. An ozone concentration of 100 g/m3 was used. Smooth, uniform zirconium oxide films were deposited at temperatures up to about 450° C. Saturation was confirmed at 350° C., and at 400° C. only slight decomposition was observed as the growth rate increased from 0.7 Å/cycle with 1 s pulses of the metal precursor to 0.8 Å/cycle with 2 s pulses.
FIG. 3 . According to ERDA, the films deposited at 350° C. were exceptionally pure (no H detected, <0.06 at. % C).FIG. 4 . XRD data is presented inFIGS. 5 a, 5 b and 5c. GIXRD data is presented inFIG. 6 . Similar characteristics were observed as with films deposited from (CpMe)2Zr(OMe)Me and O3. - Several of the deposited ZrO2 films were tested for their electrical properties. Preliminary results shown in
FIG. 7 verify that the films act as dielectrics. A film deposited at 400° C. showed a CET of 0.67-1.17 nm (6.2 nm/5.58 g/cm3). - ZrO2 is deposited by ALD from alternating pulses of (MeCp)ZrCHT or another CHT metal precursor and an oxygen source, such as O3 The substrate temperature is above 300° C.
- HfO2 is deposited on a substrate by ALD using alternating pulses of a Hf CHT precursor and an oxygen source, such as O3 at a substrate temperature of above 300° C.
- TiO2 is deposited on a substrate by ALD using alternating pulses of CpTiCHT and O3 at a substrate temperature of above 300° C.
- Synthesis of CHT metal reactant: In a 1-L flask containing 5 g of magnesium chips were added 0.5 g of anhydrous FeCl3, 30 ml of cycloheptatriene, 30 ml of THF, and, over a 1-h period to allow the warming of the stirred reaction mixture, a solution of 12 g (0.063 mol) of TiCl4 in 200 ml of THF. The mixture was stirred at room temperature over night, and the volatile products were evaporated under vacuum. Sublimation of the residue (130° C./0.05 mmHg) gave a dark solid: 24.4% yield (3.54 g); mp. 177-200° C.; 1H NMR (C6D6): 1.2-1.5 (m, CH), 1.9-2.1 (m, CH), 2.1-2.2 (m, CH), 4.2-4.4 (m, CH), 4.9-5.1 (CH, m), 5.32 (s, 7H, CH), 5.6-5.8 (m, CH); 13C{1H} NMR (C6D6): 37.34 (CH, C7-ring), 88.67 (CH, η7-C7-ring), 101.53 (CH, C7-ring), 102.33 (CH, C7-ring), 113.39 (CH, C7-ring); MS (EI, 70 eV) m/z: 278, 232, 230 [M]+, 91 [C7H7]+. The chemical structure of the synthesized CHT compound was determined to be (C7H7)Ti(C7H9)/Ti(C7H8)2. While this is believed to be accurate, identification of the structure was difficult and it was initially identified differently. Crystal structure of the synthesized precursors is shown in
FIG. 9 . TG, DTG and SDTA curves measured for (CHT)Ti(CHD) are shown inFIG. 10 . - Other transition metals precursors of formula (III), such as (C7H7)M(C7H9)/M(C7H8)2, where M is a transition metal, preferably group IVB metal such as Ti, Zr, Hf, can be synthesized using essentially the method described above for synthesis of (C7H7)Ti(C7H9)/M(C7H8)2.
- It will be appreciated by those skilled in the art that various modifications and changes can be made without departing from the scope of the invention. Similar other modifications and changes are intended to fall within the scope of the invention, as defined by the appended claims.
Claims (44)
1. A method for forming a transition metal oxide thin film on a substrate in a reaction chamber by atomic layer deposition, the method comprising:
providing a vapor phase pulse of a first metalorganic reactant comprising a CHT ligand and a transition metal to the reaction chamber such that it forms no more than a monolayer on the substrate;
removing excess first reactant from the reaction chamber;
providing a vapor phase pulse of a second reactant comprising oxygen to the reaction chamber; and
removing excess second reactant and any reaction byproducts from the reaction chamber;
wherein the providing and removing steps are repeated until a thin metal oxide film of a desired thickness and composition is obtained, wherein the substrate temperature during the providing and removing steps is above about 300° C.
2. The method of claim 1 , wherein the metalorganic reactant comprises a Group IVB metal.
3. The method of claim 1 , wherein the substrate temperature during the providing and removing steps is above about 350° C.
4. The method of claim 1 , wherein the metalorganic reactant comprises one or more of hafnium, titanium, and zirconium.
5. The method of claim 1 , wherein the metalorganic reactant is an organometallic reactant.
6. The method of claim 1 , wherein the metalorganic reactant comprises two ligands, one of which is the cycloheptatrienyl (CHT, C7H7) ligand.
7. The method of claim 6 , wherein the metalorganic reactant comprises two CHT ligands.
8. The method of claim 6 , wherein the metalorganic reactant comprises one CHT ligand and one cyclopentadienyl (Cp) ligand.
9. The method of claim 6 , wherein the metalorganic reactant does not comprise a halide.
10. The method of claim 4 , wherein the deposited thin film comprises ZrO2.
11. The method of claim 4 , wherein the deposited thin film comprises TiO2.
12. The method of claim 4 , wherein the deposited thin film comprises HfO2.
13. A method for forming a transition metal oxide thin film by atomic layer deposition on a substrate in a reaction chamber comprising:
alternately and sequentially contacting the substrate with a vapor phase reactant pulse comprising a metal reactant and a vapor phase reactant pulse comprising an oxygen reactant,
wherein the metal reactant comprises a transition metal and two ligands, one of which is a cycloheptatrienyl (CHT) ligand.
14. The method of claim 13 , wherein the metal reactant comprises a Group IVB metal.
15. The method of claim 13 , wherein the metal reactant is selected from reactants having the formula (I) RxCp-M-CHT, where RxCp represents substituted or unsubstituted cyclopentadienyl, CHT is cycloheptatrienyl and M is selected from Ti, Zr and Hf.
16. The method of claim 13 , wherein the metal reactant is selected from reactants having the formula (II) (R1R2R3R4R5R6R7)CHT-M-Cp(R8R9R10R11R12), where M is selected from Ti, Zr and Hf, and R1-12 can independently be H or an alkyl group.
17. The method of claim 13 , wherein the metal reactant is selected from reactants having the formula (III) (R1R2R3R4R5R6R7)CHT-M-CHT(R8R9R10R11R12R13R14), where M is selected from Ti, Zr and Hf, and R1-14 can independently be H or an alkyl group.
18. The method of claim 13 , wherein the metal reactant is selected from reactants having the formula (IV) R1R2R3R4R5R6R7)CHT-M-L, where M is selected from Ti, Zr and Hf; R1-7 can independently be H or an alkyl group; and L is a mono or bidentate alkyl, cycloalkyl, alkoxy, amide or imido group or acyclic or cyclic dienyl ligand.
19. The method of claim 13 , wherein the metal reactant is selected from reactants having the formula (V) R1R2R3R4R5R6R7)CHT-M-CHD(R8R9R10R11R12R13R14R15R16), where M is selected from Ti, Zr and Hf; R1-16 can independently be H or an alkyl group, and CHD is cyloheptadiene (C7H9).
20. The method of claim 13 , wherein the metal reactant is selected from reactants having the formula (VI) (R1R2R3R4R5R6R7R8)X-M-X(R9R10R11R12R13R14R15R16), where M is selected from Ti, Zr and Hf, R1-14 can independently be H or an alkyl group and X is cycloheptatriene (C7H8).
21. The method of claim 13 , wherein the oxygen reactant is selected from the group consisting of O2, O3, H2O, NO, NO2, N2O, and H2O2.
22. The method of claim 13 , wherein the substrate temperature during the pulses is from about 100 to about 500° C.
23. The method of claim 13 , wherein the substrate temperature during the pulses is above about 300° C.
24. The method of claim 13 , wherein the metal precursor comprises Ti.
25. The method of claim 13 , wherein the metal precursor comprises Hf.
26. The method of claim 13 , wherein the metal precursor comprises Zr.
27. A method for forming a thin film comprising a transition metal by atomic layer deposition on a substrate in a reaction space comprising:
alternately and sequentially contacting the substrate with a first vapor phase metal reactant pulse and a second vapor phase reactant pulse;
wherein the alternate and sequential pulses are repeated until a thin film of a desired thickness and composition is obtained and wherein the metal reactant comprises a compound comprising a transition metal and two cycloheptatriene (C7H8) ligands.
28. The method of claim 27 , wherein the metal reactant comprises a Group IVB metal.
29. The method of claim 28 , wherein the metal reactant comprises one of Ti, Hf and Zr.
30. The method of claim 27 , wherein the substrate temperature during the pulses is above about 300° C.
31. The method of claim 27 , wherein the thin film comprises a metal oxide.
32. The method of claim 31 , wherein the second reactant is an oxygen source.
33. The method of claim 32 , wherein the second reactant comprises one or more of O2, H2O, O3, NO, NO2, N2O, and H2O2.
34. The method of claim 27 , wherein the thin film comprises a metal nitride.
35. The method of claim 34 , wherein the second reactant is a nitrogen source.
36. The method of claim 35 , wherein the nitrogen source is selected from NH3, N2H2, and nitrogen containing plasma.
37. A method of synthesizing a CHT metal reactant comprising a transition metal, the method comprising forming a reaction mixture by combining a transition metal reactant with ferric chloride, cycloheptatriene and tetrahydrofuran (THF) in a flask containing magnesium chips.
38. The method of claim 37 , wherein the reaction mixture is stirred overnight.
39. The method of claim 37 , wherein the ferric chloride, cycloheptatriene and THF are first combined and then the transition metal chloride is added.
40. The method of claim 39 , wherein the transition metal chloride is added while warming the mixture.
41. The method of claim 39 , wherein the transition metal reactant is a transition metal chloride.
42. The method of claim 37 , wherein the transition metal reactant is a Group IVB metal chloride.
43. The method of claim 37 , wherein the Group IVB metal chloride is TiCl4.
44. The method of claim 37 , wherein the CHT metal reactant comprises (C7H7)M(C7H9)/M(C7H8) (CHT-M-CHD).
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US11555242B2 (en) * | 2010-02-25 | 2023-01-17 | Asm International N.V. | Precursors and methods for atomic layer deposition of transition metal oxides |
US20130309417A1 (en) * | 2012-05-16 | 2013-11-21 | Asm Ip Holding B.V. | Methods for forming multi-component thin films |
US9023427B2 (en) * | 2012-05-16 | 2015-05-05 | Asm Ip Holding B.V. | Methods for forming multi-component thin films |
WO2018112295A1 (en) * | 2016-12-16 | 2018-06-21 | The Government Of The United States Of America, As Represented By The Secretary Of The Navy | Selective oxidation of transition metal nitride layers within compound semiconductor device structures |
US10262856B2 (en) | 2016-12-16 | 2019-04-16 | The United States Of America, As Represented By The Secretary Of The Navy | Selective oxidation of transition metal nitride layers within compound semiconductor device structures |
US20220411931A1 (en) * | 2019-01-17 | 2022-12-29 | Asm Ip Holding B.V. | Methods of forming a transition metal containing film on a substrate by a cyclical deposition process |
US11959171B2 (en) * | 2019-01-17 | 2024-04-16 | Asm Ip Holding B.V. | Methods of forming a transition metal containing film on a substrate by a cyclical deposition process |
Also Published As
Publication number | Publication date |
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US9365926B2 (en) | 2016-06-14 |
US20190382887A1 (en) | 2019-12-19 |
US11555242B2 (en) | 2023-01-17 |
US9677173B2 (en) | 2017-06-13 |
US20170253966A1 (en) | 2017-09-07 |
US20160258054A1 (en) | 2016-09-08 |
US20150191817A1 (en) | 2015-07-09 |
US10344378B2 (en) | 2019-07-09 |
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