EP3947405A1 - Metal complexes for gas-phase thin-film deposition - Google Patents
Metal complexes for gas-phase thin-film depositionInfo
- Publication number
- EP3947405A1 EP3947405A1 EP20713663.1A EP20713663A EP3947405A1 EP 3947405 A1 EP3947405 A1 EP 3947405A1 EP 20713663 A EP20713663 A EP 20713663A EP 3947405 A1 EP3947405 A1 EP 3947405A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- hydra
- metal complex
- metal
- complex according
- ethyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 114
- 239000002184 metal Substances 0.000 title claims abstract description 114
- 238000000427 thin-film deposition Methods 0.000 title description 4
- QRXWMOHMRWLFEY-UHFFFAOYSA-N isoniazide Chemical compound NNC(=O)C1=CC=NC=C1 QRXWMOHMRWLFEY-UHFFFAOYSA-N 0.000 claims abstract description 98
- 241000243251 Hydra Species 0.000 claims abstract description 97
- 239000003446 ligand Substances 0.000 claims abstract description 48
- IDSMDKUVIBSETN-UHFFFAOYSA-N n-methyl-n-(propan-2-ylideneamino)methanamine Chemical compound CN(C)N=C(C)C IDSMDKUVIBSETN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 230000007935 neutral effect Effects 0.000 claims abstract description 11
- 125000000129 anionic group Chemical group 0.000 claims abstract description 8
- 150000004696 coordination complex Chemical class 0.000 claims description 92
- 238000000034 method Methods 0.000 claims description 37
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical group CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 claims description 32
- 230000008569 process Effects 0.000 claims description 31
- 239000002243 precursor Substances 0.000 claims description 28
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 23
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims description 22
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 21
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 15
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 14
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 11
- -1 methylcyclopentadienyl Chemical group 0.000 claims description 10
- 239000004215 Carbon black (E152) Substances 0.000 claims description 9
- 238000000151 deposition Methods 0.000 claims description 9
- 229930195733 hydrocarbon Natural products 0.000 claims description 9
- 229910052738 indium Inorganic materials 0.000 claims description 8
- 229910052741 iridium Inorganic materials 0.000 claims description 6
- 229910052707 ruthenium Inorganic materials 0.000 claims description 6
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 5
- 229910052733 gallium Inorganic materials 0.000 claims description 5
- 229910052732 germanium Inorganic materials 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229910052787 antimony Inorganic materials 0.000 claims description 4
- 229910052785 arsenic Inorganic materials 0.000 claims description 4
- 229910052797 bismuth Inorganic materials 0.000 claims description 4
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 4
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052714 tellurium Inorganic materials 0.000 claims description 4
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- 150000002527 isonitriles Chemical class 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 description 26
- 238000006894 reductive elimination reaction Methods 0.000 description 22
- 238000000354 decomposition reaction Methods 0.000 description 19
- 239000007789 gas Substances 0.000 description 18
- 239000012071 phase Substances 0.000 description 17
- 150000002739 metals Chemical class 0.000 description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 15
- 238000000231 atomic layer deposition Methods 0.000 description 13
- 239000000758 substrate Substances 0.000 description 13
- 238000002411 thermogravimetry Methods 0.000 description 13
- 239000010409 thin film Substances 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000007788 liquid Substances 0.000 description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 8
- 150000003624 transition metals Chemical class 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 230000009467 reduction Effects 0.000 description 7
- 239000000706 filtrate Substances 0.000 description 6
- 238000010348 incorporation Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 5
- 239000013522 chelant Substances 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 238000011065 in-situ storage Methods 0.000 description 5
- 229910052723 transition metal Inorganic materials 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000001149 thermolysis Methods 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical group [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000000859 sublimation Methods 0.000 description 3
- 230000008022 sublimation Effects 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- LAXRNWSASWOFOT-UHFFFAOYSA-J (cymene)ruthenium dichloride dimer Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Ru+2].[Ru+2].CC(C)C1=CC=C(C)C=C1.CC(C)C1=CC=C(C)C=C1 LAXRNWSASWOFOT-UHFFFAOYSA-J 0.000 description 2
- RHUYHJGZWVXEHW-UHFFFAOYSA-N 1,1-Dimethyhydrazine Chemical compound CN(C)N RHUYHJGZWVXEHW-UHFFFAOYSA-N 0.000 description 2
- MCSXGCZMEPXKIW-UHFFFAOYSA-N 3-hydroxy-4-[(4-methyl-2-nitrophenyl)diazenyl]-N-(3-nitrophenyl)naphthalene-2-carboxamide Chemical compound Cc1ccc(N=Nc2c(O)c(cc3ccccc23)C(=O)Nc2cccc(c2)[N+]([O-])=O)c(c1)[N+]([O-])=O MCSXGCZMEPXKIW-UHFFFAOYSA-N 0.000 description 2
- 241000349731 Afzelia bipindensis Species 0.000 description 2
- 241001120493 Arene Species 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 238000003776 cleavage reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000005595 deprotonation Effects 0.000 description 2
- 238000010537 deprotonation reaction Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 125000001145 hydrido group Chemical group *[H] 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- IHLVCKWPAMTVTG-UHFFFAOYSA-N lithium;carbanide Chemical compound [Li+].[CH3-] IHLVCKWPAMTVTG-UHFFFAOYSA-N 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000007017 scission Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000002076 thermal analysis method Methods 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- DHCWLIOIJZJFJE-UHFFFAOYSA-L dichlororuthenium Chemical compound Cl[Ru]Cl DHCWLIOIJZJFJE-UHFFFAOYSA-L 0.000 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- SZEJQLSRYARYHS-UHFFFAOYSA-N dimethylindium Chemical compound C[In]C SZEJQLSRYARYHS-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- KYMVBVBRCRFHIE-UHFFFAOYSA-N ethane-1,2-diimine Chemical compound N=CC=N KYMVBVBRCRFHIE-UHFFFAOYSA-N 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 125000001590 germanediyl group Chemical group [H][Ge]([H])(*)* 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- ZRKSVHFXTRFQFL-UHFFFAOYSA-N isocyanomethane Chemical compound C[N+]#[C-] ZRKSVHFXTRFQFL-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Inorganic materials [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 1
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 description 1
- 229910001623 magnesium bromide Inorganic materials 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- KGSVQMBEBWYNLB-PKNBQFBNSA-N n-methyl-n-[(e)-1-phenylethylideneamino]methanamine Chemical compound CN(C)\N=C(/C)C1=CC=CC=C1 KGSVQMBEBWYNLB-PKNBQFBNSA-N 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229960000380 propiolactone Drugs 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 238000012982 x-ray structure analysis Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F17/00—Metallocenes
- C07F17/02—Metallocenes of metals of Groups 8, 9 or 10 of the Periodic System
-
- 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
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0033—Iridium compounds
-
- 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
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0046—Ruthenium compounds
-
- 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
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
- C23C16/18—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metallo-organic compounds
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45553—Atomic layer deposition [ALD] characterized by the use of precursors specially adapted for ALD
Definitions
- the invention relates to metal complexes with acetone dimethylhydrazone ligands.
- the invention also relates to processes for the production of the metal complexes and uses of the metal complexes in CVD processes and ALD processes.
- the invention also relates to processes in which the metal complexes are used as precursors, as well as metallized surfaces obtainable with the metal complexes.
- the surface of a substrate can be metallized in various ways.
- the surface of a substrate can be metallized, for example, by means of vapor phase thin film deposition.
- CVD Chemical Vapor Deposition
- ALD atomic layer deposition
- the metal is typically present as a gaseous precursor substance.
- Such precursors are also referred to as precursors. Because they are used in the gas phase, the precursors should be as volatile as possible. Metal complexes are often used as precursors for metals.
- ruthenium or indium for example, (methylcyclopentadienyl) 2Ru, (dimethylpentadienyl ⁇ Ru, (arene) Ru (1,4-diaza-1,3-butadiene), MbbIh and [3-dimethylamino) propyl] dimethylindium are in principle suitable .
- the known precursors have various disadvantages.
- (Methylcyclopentadienyl ⁇ Ru, for example, is comparatively thermally stable and does not allow high deposition rates of ruthenium. These precursors can also lead to the incorporation of carbon.
- the precursors should be obtained in the highest possible yield.
- the precursors should have a long shelf life at room temperature.
- the precursors should withstand heating of a storage vessel for gas-phase thin-film processes such as a so-called Bubbier to temperatures of up to 100 ° C in order to increase the vapor pressure.
- the precursors should decay exothermically under typical conditions of gas phase thin-film processes, such as in particular at elevated temperatures.
- Fujisawa et al. describe cuprates with acetone dimethylhydrazone ligands and lithium or magnesium bromide as cationic species. 111 These were only formed in situ as reactants in the synthesis of 7-oxo- (E) -3-alkanoic acids by reaction with ß-vinyl-ß-propiolactone. Cardenas et al. describe palladium complexes with acetophenone dimethylhydrazone, triphenylphosphine and halido ligands. 121 S. Javed et al. describe zinc and aluminum complexes with acetone dimethylhydrazone ligands. 131 141 The decomposition behavior of these complexes, especially during thermolysis, was not investigated. Complexes of acetone dimethyl hydrazone ligands with other metals can undergo an undesired reductive elimination of the acetone dimethyl hydrazone ligands. This regularly results in an unstable complex.
- the invention is based on the object of providing metal complexes which at least partially and as far as possible completely overcome the disadvantages described above.
- the invention is based in particular on the object of providing metal complexes which have the advantageous properties described above.
- the metal complexes should have a high volatility.
- the metal complexes should be as liquid as possible at room temperature.
- the metal complexes should still be stable at higher temperatures.
- the metal complexes should not have too high a decomposition temperature.
- the object of the invention is also to ensure good synthetic accessibility of the metal complexes, in particular via syntheses with a few steps. It is also an object of the invention that the synthesis of the metal complexes does not require harsh reaction conditions and provides the highest possible yields.
- the invention relates to a metal complex of the formula (I):
- the atomic number of the metal atom M indicates the position of the metal atom M in the periodic table of the elements.
- the ordinal numbers or metals defined with areas a) to c) are accordingly the following: a) 12 (Mg), 21 (Sc), 22 (Ti), 23 (V), 24 (Cr), 25 (Mn), 26 (Fe), 27 (Co), 28 (Ni), 29 (Cu ), 31 (Ga), 32 (Ge), 33 (As) and 34 (Se);
- the metal atom M does not have the atomic number 30 (Zn; M is not zinc), not the atomic number 48 (Cd; M is not cadmium) and not the atomic number 80 (Hg; M is not mercury).
- the metal atom M can have different oxidation states, preferably the oxidation state + 1, + II, + III, + IV, + V, + VI or + VII.
- the metal complex according to the invention is a mononuclear metal complex with a metal atom M.
- the metal complex according to the invention is a dinuclear metal complex with two metal atoms M.
- the two metal atoms preferably have the same atomic number.
- the metal complex is a homodinuclear metal complex.
- the total charge of the metal complex is 0 (zero), ie the metal complex is electrically neutral.
- the neutrality of the metal complex is reflected in the lack of charge information on the square brackets.
- the ligand (hydra) is an acetone dimethylhydrazone monoanion.
- (hydra) is a monoanion derived from acetone dimethylhydrazone by deprotonation. The negative charge of the monoanion is delocalized in (hydra).
- (hydra) is sometimes also referred to here as “[hydra] (1-)” or “Hydra”.
- Acetone dimethylhydrazone is sometimes also referred to as “H-hydra”.
- Known metal complexes with the ligand (hydra) are formed by metals that do not have two stable oxidation states, the difference of which is two charges, or whose d-shell is fully occupied (Li, Al and Zn). Such (hydra) metal complexes do not tend to undergo reductive elimination of (hydra). A stability of such complexes is to be expected accordingly.
- a ligand (hydra) is present in addition to at least one further ligand R.
- (hydra) can be eliminated reductively together with the at least one further ligand R.
- R is preferably H, alkyl or also (hydra).
- reductive elimination of R- (hydra) can occur according to the following scheme:
- R R H, alkyl, hydra
- the reductive elimination forms a selective, thermal decomposition route.
- the reductive elimination of R-hydra reduces M.
- M can be deposited metallic. Because of this assumed path of decomposition, the metal complexes according to the invention are particularly suitable for gas-phase thin-film processes for metallizing substrate surfaces.
- the metal complexes of the invention include complexes of transition metals. These metal complexes are formed by transition metal atoms M with an atomic number from 21 to 29, 39 to 47 or 71 to 79. Particularly preferred metal atoms are Ti, Co, Ru, Pd, Ir and Au. These transition metal atoms have unoccupied or partially occupied d orbitals. That is, the transition metal atoms have a d-electron configuration from d ° to d 9 . For complexes according to the invention with the transition metals mentioned, a selective, thermal decomposition via reductive elimination of R-hydra is expected.
- Transition metals with a fully occupied d-shell, ie with ad 10 -electronic configuration, are not included according to the invention.
- (hydra) -metal complexes of transition metals with d 10 electron configuration behave similarly to (hydra) -metal complexes of main group metals of the 2nd and 3rd period, in particular, due to their closed, stable d 10 shell from Li and AI.
- Such (hydra) metal complexes regularly do not undergo reductive elimination of R- (hydra).
- M Zn with d 10 electron configuration, neither reductive eliminations nor use in gas phase thin-film processes are known.
- the metal complexes according to the invention also include complexes of main group metals of the p-block, especially the 3rd, 4th, 5th and 6th periods of the periodic table of the elements. These are formed by main group metal atoms M with an atomic number of 12, 31 to 34, 49 to 52 or 81 to 83. Particularly preferred metal atoms M are Ga, Ge, As, Se, In, Sb, Te and Bi. For complexes according to the invention of these main group metals with the ligand (hydra), selective thermal decomposition via reductive elimination of R- (hydra) is expected.
- M in the metal complex is selected from Ti, Co, Ga, Ge, As, Se, Ru, Pd, In, Sb, Te, Ir, Au and Bi, more preferably selected from Co, Ga, Ge , Ru, In and Ir.
- a metal complex can serve to coat substrate surfaces with a particularly advantageous metal. With such a coating, such a metal complex can lead to particularly low rates of incorporation of carbon and other impurities.
- a reductive elimination of (hydra) with reduction of Ti, Co, Ga, Ge, As, Se, Ru, Pd, In, Sb, Te, Ir, Au or Bi can more easily take place during decomposition.
- the metal complex U and L 2 are selected independently of one another from Cl, H, methyl, ethyl, propyl, isopropyl, tert-butyl, cyclopentadienyl, methylcyclopentadienyl, isopropylcyclopentadienyl, arene, phosphine, isonitrile and carbonyl.
- a metal complex can be volatile due to the selected ligands and liquid at room temperature.
- Such a metal complex can be stabilized by the selected ligands.
- arene is an aromatic hydrocarbon.
- Arenes are p-acidic compounds. Arenes include both monocyclic and polycyclic aromatic hydrocarbons.
- An arene used according to the invention can optionally be substituted.
- Optional substituents of the arene are sometimes referred to here with (R 1 ) m .
- the index m can preferably be 0, 1, 2, 3, 4, 5 or 6, more preferably 0 or 2, particularly preferably 2.
- R 1 is preferably selected from hydrocarbon radicals, hydroxyl groups, alkoxy groups, amino groups and halogens, more preferably from Hydrocarbon residues.
- a hydrocarbon radical refers, as usual, to a radical which is composed exclusively of carbon and hydrogen.
- a hydrocarbon radical generally refers to a hydrocarbon radical which can be saturated or unsaturated. Saturated hydrocarbon radicals are preferred.
- a hydrocarbon radical generally refers to a hydrocarbon radical which can be linear, branched or cyclic. Linear and branched hydrocarbon radicals are preferred.
- a metal complex can be more easily accessible synthetically.
- the ligands L 1 and L 2 can be suitably selected depending on the metal atom M in order to stabilize the metal complex on the one hand and to ensure its volatility on the other hand.
- reductive elimination of (hydra) can more easily take place on decomposition.
- n 1.
- Such a preferred metal complex has the formula (Ia).
- the metal complex of the formula (Ia) can be very volatile and liquid at room temperature, but still stable at higher temperatures.
- the metal complex of the formula (Ia) cannot have too high a decomposition temperature.
- the metal complex of the formula (Ia) can be accessible synthetically over a few steps. In the case of the metal complex of the formula (Ia), a reductive elimination of (hydra) can more easily take place on decomposition.
- the arene is a C s (Ci , 2 , 3 , 4 , 5 , C 1, 2, 3, 4, 5, 6) identical or different 6 , 7 , 8) hydrocarbon radicals substituted arene or an unsubstituted arene.
- the arene is more preferably selected from 4-isopropyltoluene and benzene.
- 4-Isopropyltoluene is also known as p-cymene or para-cymene. Without being bound by theory, it is expected that the asymmetrically substituted 4-isopropyltoluene in particular makes crystallization of the metal complex of the formula (Ia) more difficult and improves its volatility and fluidity at room temperature.
- Such a preferred metal complex has the formula (Ib).
- the metal complex of the formula (Ib) can be very volatile and liquid at room temperature, but still stable at higher temperatures.
- the metal complex of the formula (Ib) cannot have too high a decomposition temperature.
- the metal complex of the formula (Ib) can be obtained synthetically in a few steps. In the case of the metal complex of the formula (Ib), a reductive elimination of (hydra) can more easily take place on decomposition.
- the metal complex according to the invention is preferably a metal complex of the formula (Ia) or a metal complex of the formula (Ib).
- Metal complexes which are particularly preferred according to the invention are [RuCl (p-cymene) (hydra)], [RuMe (p-cymene) (hydra)] and [InMe2 (hydra)] 2.
- a 1, 4-C, N-coordination mode, a 1, 3-C, N-coordination mode and a 1, 2-N, N-coordination mode are shown.
- the ligand (hydra) can help to stabilize volatile and / or metastable metal complexes. Without being bound by theory, it is assumed that the ligand (hydra) can stabilize volatile and / or metastable metal complexes, in particular via a CnN chelate ring configuration.
- the increased stability improves the suitability of corresponding metal complexes for gas phase thin-film processes.
- the increased stability improves in particular the suitability of corresponding metal complexes for the metallization of substrate surfaces by means of CVD or ALD processes.
- the metal complex (hydra) is coordinated to M via an sp 3 -hybridized N atom.
- a coordination can favor a CnN chelate ring configuration in the metal complex according to the invention.
- a CHN chelate ring configuration can help stabilize the metal complex.
- the metal complex (hydra) it is coordinated to M via an sp 2 hybridized N atom.
- Such coordination can favor alternative chelate ring configurations in the metal complex according to the invention.
- Alternative chelate ring configurations can contribute to a greater structural diversity and thus a greater variability in the physicochemical properties of the metal complexes according to the invention.
- dinuclear metal complexes are also encompassed, the bridging (r
- (hydra) can simultaneously coordinate to two metal atoms M with preferably the same atomic number. In the case of two metal atoms M having the same atomic number, a homodinuclear dimer results.
- the two metal atoms M together with the (hydra) ligands can, for example, form an eight-membered ring.
- the metal complex is liquid under standard conditions.
- Standard conditions are a temperature of 25 ° C and an absolute pressure of 1 ⁇ 10 5 Pa.
- the aggregate state “liquid” includes an oily consistency of the metal complex. Liquid the metal complex under standard conditions can improve the suitability of the metal complex for gas phase thin film processes.
- the metal complex decomposes at temperatures in the range from 100 to 200.degree. C., more preferably in the range from 120 to 180.degree. C., and even more preferably in the range from 140 to 160.degree. Decomposition of the metal complex at these temperatures can improve the suitability of the metal complex for gas phase thin film processes.
- the onset of a decomposition of a metal complex according to the invention is determined by thermal analysis.
- the thermal analysis is preferably a thermogravimetric analysis (TGA).
- TGA thermogravimetric analysis
- Thermogravimetric analysis is an analytical method in which changes in the mass of a sample are measured as a function of temperature and time. In thermogravimetric analysis, the sample is heated in a crucible. A holder of the crucible is coupled to a scale which registers changes in mass during the heating process. If there is a reduction in mass during the heating process, this can indicate the disintegration of the sample.
- the TGA takes place, for example, in a temperature range of 25 ° C to 800 ° C.
- the heating rate for TGA is typically 10 ° C / min.
- the mass degradation caused by evaporation and / or decomposition is preferably monitored using TGA and a simultaneous differential thermal analysis (SDTA).
- SDTA determines the heat flow on the basis of endothermic peaks (e.g. melting point, evaporation from the liquid phase, sublimation below the melting point) or exothermic peaks (e.g. exothermic decomposition reaction).
- An endothermic peak with no loss of mass regularly corresponds to a melting point.
- An endothermic peak with a loss of mass regularly corresponds to an evaporation.
- an exothermic peak with a loss of mass regularly corresponds to decomposition.
- onset values For example, the temperature of a TGA / SDTA can be specified at which the mass of the examined sample of the metal complex is degraded by 3% by weight (3% degradation).
- TM A the temperature of a TGA / SDTA can be specified at which, after the initial mass reduction of the examined sample by 3% by weight, there is a further mass reduction.
- thermogravimetric analysis the temperature of the first mass degradation of 3% by weight of the metal complex at 1 ⁇ 10 5 Pa in the range from 100 to 200 ° C., more preferably in the range from 120 to 180 ° C. and even more more preferably in the range of 140 to 160 ° C.
- the invention also relates to a method for producing a metal complex according to the invention comprising the steps:
- the process according to the invention can provide a metal complex according to the invention having the above-mentioned desired properties in a simple synthesis under mild conditions and over a few steps on an industrial scale with high yields.
- L 2 is either H, methyl, ethyl, propyl, isopropyl or tert-butyl or, following step (ii), in a step (iii) in H, methyl, ethyl, propyl, Isopropyl or tert-butyl is transferred.
- the ligand L 2 can easily be synthetically incorporated into the metal complex according to the invention be introduced.
- the ligand L 2 can provide metal complexes with an advantageous tendency towards reductive elimination of (hydra) on decomposition.
- the invention also relates to the use of a metal complex according to the invention for depositing the metal in a CVD process or an ALD process.
- This use according to the invention enables the metal to be deposited in the form of thin layers.
- the incorporation of carbon and other impurities can be minimized or avoided.
- the invention also relates to a method in which a metal complex according to the invention is used as a precursor for producing a layer from the metal.
- the layer of metal can be produced in the form of a thin layer.
- the incorporation of carbon and other impurities can be minimized or avoided.
- the invention also provides a metallized surface, obtainable by depositing a metal on a surface from a gas phase, which comprises a metal complex according to the invention.
- a metallized surface can be provided in which the incorporation of carbon and other impurities is minimized or completely avoided.
- H-hydra Acetone dimethylhydrazone
- H-hydra can be prepared, for example, by reacting equimolar amounts of acetone and / ⁇ /, / ⁇ / - dimethylhydrazine with the addition of MgSCU to scavenge the H2O formed.
- the mixture can be heated under reflux conditions for 7 hours: , NMe 2
- H-hydra is a non-air-sensitive, distillable liquid and CH acid.
- H-hydra is preferably converted into the deprotonated (lithiated) ligand Li (hydra).
- the deprotonation of H-hydra can take place in situ.
- H-hydra is presented in THF, for example.
- H-hydra can then be deprotonated with n-BuLi, for example.
- Such reactions in situ are known.
- Li (hydra) be prepared by adding H-hydra in n-hexane at 0 ° C. with the dropwise addition of an nBuLi solution. The resulting solid can be separated off by means of filtration and dried in a fine vacuum.
- a mixture of isomers of Li (hydra) is regularly obtained:
- the invention includes that the N-amino-enamide form or enhydrazide form described below is present in such a mixture of isomers:
- the deprotonated (lithiated) ligand Li (hydra) is subsequently used to prepare hydra-metal complexes according to the invention.
- metal complexes of the formula [(arene) RuCI (hydra)] are described by way of example (the arene ligand is preferably benzene or para-cymene):
- the chlorido ligand on the ruthenium can subsequently preferably be substituted.
- the substitution can take place with equimolar amounts of MeLi for the purpose of introducing a methyl group.
- the substitution can be made with 0.3 equivalents of LiAlhU for the purpose of introducing a hydrido ligand.
- both cases may be worked up as follows: removal of the solvent under high vacuum, taking the residue up in n-hexane, filtration through Celite ®, drying of the filtrate under high vacuum (FV), and isolating the target compounds by recondensation (FV / 100 ° C) from the obtained Residues.
- the following exemplary reaction scheme can be given:
- L N 2-electron neutral ligand, preferably CO, CNMe, PH3
- the metal complexes with (hydra) ligand that can be prepared according to the invention are regularly metastable, volatile and readily vaporizable complexes. They are therefore particularly suitable as precursors in gas phase thin-film processes such as CVD and ALD.
- the preferred synthetic routes given here by way of example yield inexpensive, easily accessible metal complexes that can be isolated on a large scale in analytically pure form.
- the metal complexes according to the invention are used as precursors for metals or metal layers.
- they can be used for the production of thin films from a metal by means of gas phase thin film processes such as CVD and ALD.
- Gas phase thin film processes involve a gas phase reaction that typically occurs on or near a surface of a substrate.
- the reactants or precursors involved in the reaction are fed to the substrate to be coated in the form of gases.
- the substrate is arranged in a reaction chamber and is heated. Most of the preheated gases are thermally activated by the heated substrate and react with one another or with the substrate. Precursors contained in the gases are thermally decomposed by the heated substrate. As a result, the desired material is deposited and chemically bound. Chemisorption of the desired material occurs, along with the metal in the present invention the ordinal number selected from the ranges a) 21 to 33, with the exception of 30, b) 39 to 51, with the exception of 48, and c) 71 to 83, with the exception of 80.
- the ALD process also known as atomic layer deposition, is a modified CVD process.
- the reaction or sorption on the surface ends by itself after the surface is completely covered. This self-limiting reaction is carried out in several cycles, which are limited by intermediate flushing steps. In this way, very exact layer thicknesses are achieved.
- the metal complexes according to the invention can be prepared by an inexpensive technical synthesis.
- the simple technical synthesis is an important advantage in an industrial application of the metal complexes according to the invention in processes of gas phase deposition.
- Another important reason for the particular suitability of the metal complexes according to the invention for CVD and / or ALD processes is that the metal complexes according to the invention are volatile compounds, some of which are liquid at room temperature.
- they can be successfully decomposed into the corresponding elemental metal. They therefore represent an advantageous alternative to known precursors for the corresponding metals for the deposition of such elementary metals.
- Acetone dimethylhydrazone (14.8 g, 147 mmol, 1.0 eq) was treated with n hexane (100 ml) and the mixture was cooled to 0 ° C.
- An nBuLi solution (2.43 M in nHexane, 60.5 ml, 147 mmol, 1.0 eq) was added via a dropping funnel over a period of two hours, the precipitation of a colorless solid being observed.
- the mixture was stirred overnight, allowing it to warm to room temperature.
- the resulting solid was separated off by filtration, washed with n-hexane (30 ml) and finally dried in vacuo. Li (hydra) could be obtained as a colorless solid.
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