CN114989226A - Platinum precursor, and preparation method and application of trimethyl cyclopentadienyl platinum - Google Patents
Platinum precursor, and preparation method and application of trimethyl cyclopentadienyl platinum Download PDFInfo
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- CN114989226A CN114989226A CN202210830414.1A CN202210830414A CN114989226A CN 114989226 A CN114989226 A CN 114989226A CN 202210830414 A CN202210830414 A CN 202210830414A CN 114989226 A CN114989226 A CN 114989226A
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- platinum
- cyclopentadienyl
- halide
- trimethyl
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 144
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 86
- YGBYJRVGNBVTCQ-UHFFFAOYSA-N C[Pt](C)C.[CH]1C=CC=C1 Chemical compound C[Pt](C)C.[CH]1C=CC=C1 YGBYJRVGNBVTCQ-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 239000002243 precursor Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 48
- -1 platinum halide Chemical class 0.000 claims abstract description 87
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 27
- 150000001350 alkyl halides Chemical class 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000012022 methylating agents Substances 0.000 claims abstract description 23
- 238000005727 Friedel-Crafts reaction Methods 0.000 claims abstract description 16
- 239000002841 Lewis acid Substances 0.000 claims abstract description 16
- 150000007517 lewis acids Chemical class 0.000 claims abstract description 16
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 14
- 239000012298 atmosphere Substances 0.000 claims abstract description 11
- 230000001681 protective effect Effects 0.000 claims abstract description 10
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 claims description 26
- DODHYCGLWKOXCD-UHFFFAOYSA-N C[Pt](C1(C=CC=C1)C)(C)C Chemical group C[Pt](C1(C=CC=C1)C)(C)C DODHYCGLWKOXCD-UHFFFAOYSA-N 0.000 claims description 25
- 238000010791 quenching Methods 0.000 claims description 24
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 22
- 230000000171 quenching effect Effects 0.000 claims description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 20
- FBEIPJNQGITEBL-UHFFFAOYSA-J tetrachloroplatinum Chemical group Cl[Pt](Cl)(Cl)Cl FBEIPJNQGITEBL-UHFFFAOYSA-J 0.000 claims description 14
- 229940102396 methyl bromide Drugs 0.000 claims description 13
- DBKDYYFPDRPMPE-UHFFFAOYSA-N lithium;cyclopenta-1,3-diene Chemical compound [Li+].C=1C=C[CH-]C=1 DBKDYYFPDRPMPE-UHFFFAOYSA-N 0.000 claims description 12
- 239000000741 silica gel Substances 0.000 claims description 12
- 229910002027 silica gel Inorganic materials 0.000 claims description 12
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 claims description 11
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 8
- IZWIPIIVPHXLTN-UHFFFAOYSA-N potassium;cyclopenta-1,3-diene Chemical compound [K+].C1C=CC=[C-]1 IZWIPIIVPHXLTN-UHFFFAOYSA-N 0.000 claims description 8
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- OHUVHDUNQKJDKW-UHFFFAOYSA-N sodium;cyclopenta-1,3-diene Chemical compound [Na+].C=1C=C[CH-]C=1 OHUVHDUNQKJDKW-UHFFFAOYSA-N 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- 230000011987 methylation Effects 0.000 claims description 4
- 238000007069 methylation reaction Methods 0.000 claims description 4
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims 3
- 239000011541 reaction mixture Substances 0.000 claims 3
- 230000000694 effects Effects 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 7
- BCSYXDNNYLPNJO-UHFFFAOYSA-M C[Pt](C)(C)I Chemical compound C[Pt](C)(C)I BCSYXDNNYLPNJO-UHFFFAOYSA-M 0.000 abstract description 6
- 238000009776 industrial production Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 230000001035 methylating effect Effects 0.000 abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 69
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 38
- 239000000203 mixture Substances 0.000 description 19
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 19
- 239000000047 product Substances 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 238000001816 cooling Methods 0.000 description 15
- 239000013078 crystal Substances 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 11
- FSKLOGLSYZIRMP-UHFFFAOYSA-N carbanide 2-methylcyclopenta-1,3-diene platinum(4+) Chemical compound [CH3-].[CH3-].[CH3-].[Pt+4].CC=1C=C[CH-]C=1 FSKLOGLSYZIRMP-UHFFFAOYSA-N 0.000 description 8
- 238000005229 chemical vapour deposition Methods 0.000 description 8
- 238000001704 evaporation Methods 0.000 description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 7
- 230000029936 alkylation Effects 0.000 description 7
- 238000005804 alkylation reaction Methods 0.000 description 7
- 239000012300 argon atmosphere Substances 0.000 description 7
- 239000006227 byproduct Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 239000012074 organic phase Substances 0.000 description 7
- 238000000746 purification Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000012043 crude product Substances 0.000 description 6
- VMFHCJPMKUTMMQ-UHFFFAOYSA-N cyclopenta-2,4-dien-1-yl(trimethyl)silane Chemical compound C[Si](C)(C)C1C=CC=C1 VMFHCJPMKUTMMQ-UHFFFAOYSA-N 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 150000004820 halides Chemical class 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- NXPHGHWWQRMDIA-UHFFFAOYSA-M magnesium;carbanide;bromide Chemical compound [CH3-].[Mg+2].[Br-] NXPHGHWWQRMDIA-UHFFFAOYSA-M 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- VYNCPPVQAZGELS-UHFFFAOYSA-N toluene;trimethylalumane Chemical compound C[Al](C)C.CC1=CC=CC=C1 VYNCPPVQAZGELS-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000000859 sublimation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 1
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- QNGLIBBVTNARBG-UHFFFAOYSA-N 1-methylcyclopenta-1,3-diene;sodium Chemical compound [Na].CC1=CC=CC1 QNGLIBBVTNARBG-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 1
- CONKBQPVFMXDOV-QHCPKHFHSA-N 6-[(5S)-5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-2-oxo-1,3-oxazolidin-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C[C@H]1CN(C(O1)=O)C1=CC2=C(NC(O2)=O)C=C1 CONKBQPVFMXDOV-QHCPKHFHSA-N 0.000 description 1
- GNTLCIZVDCHEHW-UHFFFAOYSA-M C1(C=CC=C1)[Pt]Cl Chemical compound C1(C=CC=C1)[Pt]Cl GNTLCIZVDCHEHW-UHFFFAOYSA-M 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 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
- 238000005468 ion implantation Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 238000000678 plasma activation Methods 0.000 description 1
- SNPHNDVOPWUNON-UHFFFAOYSA-J platinum(4+);tetrabromide Chemical compound [Br-].[Br-].[Br-].[Br-].[Pt+4] SNPHNDVOPWUNON-UHFFFAOYSA-J 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- RNJPWBVOCUGBGY-UHFFFAOYSA-J tetraiodoplatinum Chemical compound [I-].[I-].[I-].[I-].[Pt+4] RNJPWBVOCUGBGY-UHFFFAOYSA-J 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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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
- 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
- C07F15/0086—Platinum compounds
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
- C23C16/08—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 metal halides
- C23C16/14—Deposition of only one other metal element
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
- C23C16/18—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metallo-organic compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
Abstract
The invention relates to a platinum precursor, a preparation method and application of trimethyl cyclopentadienyl platinum. The preparation method of the platinum precursor comprises the following steps: reacting platinum halide with cyclopentadienyl alkali metal salt under a protective atmosphere to prepare cyclopentadienyl platinum halide; reacting cyclopentadienyl platinum halide with a methylating agent to prepare trimethyl cyclopentadienyl platinum; under the existence of Lewis acid, trimethyl cyclopentadienyl platinum and alkyl halide are subjected to Friedel-crafts reaction to prepare a platinum precursor. The preparation method of the platinum precursor has simple process, high material activity in each step of reaction, no need of large excess of methylating reagent, and in addition, the method also reduces various complex dangerous operations generated by preparing trimethyl platinum iodide, improves the safety coefficient of the reaction and provides possibility for industrial production.
Description
Technical Field
The invention relates to the field of organic metal compounds, in particular to a platinum precursor, a preparation method and application of trimethyl cyclopentadienyl platinum.
Background
The precursor is one of the important materials for manufacturing chips, and is mainly used for vapor deposition coating processes, including Physical Vapor Deposition (PVD), Chemical Vapor Deposition (CVD), atomic vapor deposition (ALD), and the like, to form various thin film layers meeting the semiconductor manufacturing requirements, and also for semiconductor epitaxial growth, etching, ion implantation doping, cleaning, and the like.
Chemical vapor deposition is a technique for depositing a thin film of metal on a surface. In chemical vapor deposition, chemical vapor deposition precursors, also known as chemical vapor deposition compounds, decompose by thermochemical, photochemical or plasma activation to form a film having a desired composition. For example, a chemical vapor deposition precursor can be contacted with a substrate heated above the decomposition temperature of the precursor to form a metal or metal oxide film on the substrate.
Trimethyl (methylcyclopentadienyl) platinum (IV) compounds ((MeCp) PtMe) 3 ) Is a promising precursor for platinum chemical vapor deposition. The compound is reported to be stable to air, water and temperatures below 150 ℃. In addition, as (MeCp) PtMe 3 Platinum nanocrystals, which have excellent catalytic activity in the hydrogen-silicon addition, can be repeatedly prepared in a coordinating solvent (e.g., ethylene glycol, glycerol) or a non-coordinating solvent (e.g., diphenylmethane) by conventional heating, photolysis, or microwave irradiation as a starting material.
The conventional preparation process of trimethyl (methylcyclopentadienyl) platinum (IV) compounds is as follows: reacting potassium platinochloride serving as a raw material with excessive methyllithium, then quenching with 1, 2-dibromoethane, adding potassium iodide to obtain an intermediate trimethyl platinum iodide, finally reacting with methyl cyclopentadiene sodium salt or lithium salt, and purifying to obtain a target product. In the method, the methyl lithium is greatly excessive, so that quenching operation is difficult, and industrial amplification is difficult to realize due to the safety problem in the process of preparing trimethyl platinum iodide.
Disclosure of Invention
In view of this, it is necessary to provide a method for preparing a platinum precursor with a simple process and a high safety factor.
In addition, a preparation method of trimethylcyclopentadienyl platinum and a preparation method of a metal thin film are also needed to be provided.
A preparation method of a platinum precursor comprises the following steps:
reacting platinum halide with cyclopentadienyl alkali metal salt in a protective atmosphere to prepare cyclopentadienyl platinum halide;
reacting the cyclopentadienyl platinum halide with a methylating agent to prepare trimethyl cyclopentadienyl platinum;
and carrying out Friedel-crafts reaction on the trimethylcyclopentadienyl platinum and the alkyl halide in the presence of Lewis acid to prepare a platinum precursor.
In one embodiment, the cyclopentadienyl alkali metal salt is selected from at least one of cyclopentadienyl lithium, cyclopentadienyl sodium and cyclopentadienyl potassium.
In one embodiment, the platinum halide is platinum tetrachloride.
In one embodiment, the methylating agent is selected from at least one of methyllithium and trimethylaluminum.
In one embodiment, the alkyl halide is at least one selected from methyl bromide and methyl iodide, and the platinum precursor is trimethyl (methylcyclopentadienyl) platinum.
In one embodiment, after the step of performing friedel-crafts reaction on the trimethylcyclopentadienylplatinum and the alkyl halide, the method further comprises the following steps:
adding a quenching agent into a system after the Friedel-crafts reaction to quench the reaction, and then passing through a silica gel column, removing a solvent, and sublimating and purifying.
In one embodiment, the molar ratio of the platinum halide to the cyclopentadienyl alkali metal salt is 1 (1.1-1.5).
In one embodiment, in the step of reacting platinum halide with the cyclopentadienyl alkali metal salt, the reaction temperature is-10 ℃ to 0 ℃, and the reaction time is 30min to 120 min.
In one embodiment, the molar ratio of the cyclopentadienyl platinum halide to the methyl in the methylating agent is 1 (3.3-3.6).
In one embodiment, the step of reacting the cyclopentadienyl platinum halide with a methylating agent comprises: the methylation reagent is added into the cyclopentadienyl platinum halide at the temperature of 0-25 ℃, and then the reaction is carried out for 12-24 h at the temperature of 10-30 ℃.
In one embodiment, the molar ratio of the trimethylcyclopentadienyl platinum to the Lewis acid and the alkyl halide is 1 (0.1-0.5) to 1.5-2.
In one embodiment, the step of subjecting the trimethylcyclopentadienylplatinum to a friedel-crafts reaction with an alkyl halide comprises: adding the trimethylcyclopentadienyl platinum into the mixture system of the Lewis acid and the alkyl halide at the temperature of 0-30 ℃, and then reacting for 12-24 h at the temperature of 10-30 ℃.
In one embodiment, the lewis acid is selected from at least one of aluminum trichloride, iron trichloride, tin tetrachloride, and zinc chloride.
A preparation method of trimethyl cyclopentadienyl platinum comprises the following steps:
reacting platinum halide with cyclopentadienyl alkali metal salt under a protective atmosphere to prepare cyclopentadienyl platinum halide; and
and reacting the cyclopentadienyl platinum halide with a methylating agent to prepare trimethyl cyclopentadienyl platinum.
A preparation method of a metal film comprises the following steps:
preparing a platinum precursor by adopting the preparation method; and
the platinum precursor is decomposed to form a film on the substrate.
The preparation method takes platinum halide as a raw material, and the platinum halide reacts with cyclopentadienyl alkali metal salt under the protective atmosphere to obtain cyclopentadienyl platinum halide; then reacting with a methylating agent to generate trimethyl cyclopentadienyl platinum; finally, under the action of Lewis acid, Friedel-crafts reaction is carried out on the platinum precursor and alkyl halide to prepare a platinum precursor, and when the alkyl halide is methyl halide, a target product trimethyl (methyl cyclopentadienyl) platinum (IV) can be obtained. The method has simple process, high material activity in each step of reaction, no need of large excess of methylating reagent, and reduced complex dangerous operations caused by preparation of trimethyl platinum iodide, improved safety coefficient of reaction, and possibility of industrial production.
Drawings
FIG. 1 is a diagram of trimethyl (methylcyclopentadienyl) platinum prepared in example 1 1 HNMR spectrogram;
FIG. 2 is a graph of trimethyl (methylcyclopentadienyl) platinum prepared in example 1 13 CNMR spectrogram;
FIG. 3 is a graph of trimethyl (methylcyclopentadienyl) platinum prepared in example 2 1 HNMR spectrogram;
FIG. 4 is a graph of trimethyl (methylcyclopentadienyl) platinum prepared in example 2 13 CNMR spectrogram;
FIG. 5 is a graph of trimethyl (methylcyclopentadienyl) platinum prepared in example 3 1 HNMR spectrogram;
FIG. 6 is a graph of trimethyl (methylcyclopentadienyl) platinum prepared in example 3 13 CNMR spectrogram;
FIG. 7 is a graph of trimethyl (methylcyclopentadienyl) platinum prepared in example 4 1 HNMR spectrogram;
FIG. 8 is a graph of trimethyl (methylcyclopentadienyl) platinum prepared in example 4 13 CNMR spectrogram;
FIG. 9 is a photograph of trimethyl (methylcyclopentadienyl) platinum prepared in example 5 1 HNMR spectrogram;
FIG. 10 is a graph of trimethyl (methylcyclopentadienyl) platinum prepared in example 5 13 CNMR spectrogram.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the following description taken in conjunction with the accompanying drawings. The detailed description sets forth the preferred embodiments of the invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
Herein, room temperature means a temperature of 10 ℃ to 30 ℃.
Aiming at the problems of complex operation, high risk, difficult industrial application and the like in the traditional preparation process of trimethyl (methylcyclopentadienyl) platinum (IV), the invention provides the preparation method which has simple process and high safety and can realize industrial production.
Specifically, a method for preparing a platinum precursor according to an embodiment includes the steps of:
step S110: under the protection atmosphere, reacting platinum halide with cyclopentadienyl alkali metal salt to prepare cyclopentadienyl platinum halide.
Wherein the platinum halide is platinum tetrachloride (PtCl) 4 ). The platinum tetrachloride is cheap and easy to obtain, has wide sources and is beneficial to reducing the cost. Further, platinum tetrabromide and platinum tetraiodide have high activities, and impurities substituted with two cyclopentadienes are easily generated. Therefore, in the present embodiment, the platinum halide is preferably platinum tetrachloride.
Specifically, the protective atmosphere may be nitrogen, argon, helium, or the like.
In some embodiments, the cyclopentadienyl alkali metal salt is selected from cyclopentadienyl lithium (formula C) 5 H 5 Li, commonly abbreviated as CpLi, where Cp − Is cyclopentadiene anion), sodium cyclopentadienyl (chemical formula is C) 5 H 5 Na, commonly abbreviated as CpNa) and cyclopentadienyl potassium (formula C) 5 H 5 K, often abbreviated CpK). Experiments prove that in the preparation process of cyclopentadienyl platinum halide, the cyclopentadienyl alkali metal salt has higher reaction activity than other substances, such as cyclopentadienyl trimethyl silicon. The cyclopentadienyl trimethyl silicon hardly reacts due to insufficient activity, so that the cyclopentadienyl trimethyl silicon is difficult to obtainThe target product. The cyclopentadienyl lithium, the cyclopentadienyl sodium and the cyclopentadienyl potassium are adopted as cyclopentadienyl alkali metal salts, so that a target product with high yield can be obtained, and the final product is dark in color due to strong alkalinity of the cyclopentadienyl sodium and the cyclopentadienyl potassium. In addition, cyclopentadienyl lithium is preferably selected in consideration of ease of preparation.
Specifically, the cyclopentadienyl platinum halide has the formula CpPtX 3 Structural formula is
. Reacting platinum halide with cyclopentadienyl alkali metal salt to prepare cyclopentadienyl platinum halide, wherein the reaction formula is as follows: PtX 4 +CpY→CpPtX 3 + YX, wherein Y is an alkali metal, such as Li, Na, K, etc., and X is a halogen, such as Cl, etc.
In some embodiments, the molar ratio of platinum halide to cyclopentadienyl alkali metal salt is 1 (1.1-1.5). In a specific example, the molar ratio of platinum halide to cyclopentadienyl alkali metal salt is 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, or a range consisting of any two of these values.
In some embodiments, the step of reacting platinum halide with the cyclopentadienyl alkali metal salt is carried out at a temperature of-10 ℃ to 0 ℃ for 30min to 120 min. In one specific example, the step of reacting the platinum halide with the cyclopentadienyl alkali metal salt is carried out at a temperature in the range of-10 ℃, -8 ℃, -5 ℃, -3 ℃, -1 ℃, 0 ℃ or any two of these values. The reaction time is 30min, 45min, 60min, 75min, 90min, 105min, 120min or the range formed by any two of the values.
Further, in some embodiments, the step of reacting the platinum halide with the cyclopentadienyl alkali metal salt under a protective atmosphere comprises:
under the protective atmosphere, cooling the solution containing platinum halide to-10-0 ℃, then adding the solution containing cyclopentadienyl alkali metal salt, and continuing to react for 30-120 min at the temperature.
In a specific example, the solution containing platinum halide and the solution containing cyclopentadienyl alkali metal salt are tetrahydrofuran solutions. It is understood that the solution containing platinum halide and the solution containing cyclopentadienyl alkali metal salt are not limited to the tetrahydrofuran solution.
Step S120: reacting cyclopentadienyl platinum halide with a methylating agent to produce trimethylcyclopentadienyl platinum.
In some embodiments, the methylating agent is selected from methyllithium (CH) 3 Li) and trimethylaluminum (Al (CH) 3 ) 3 ) At least one of (a). Experiments prove that in the methylation reagent: methyl magnesium bromide is less reactive than methyl lithium and trimethylaluminum. The yield and appearance of the product prepared from trimethylaluminum are better than those of methyllithium. Therefore, in the present embodiment, the methylating agent is preferably trimethylaluminum.
In some embodiments, the molar ratio of the cyclopentadienyl platinum halide to the methyl group in the methylating agent is 1 (3.3-3.6). In a specific example, the molar ratio of the platinum cyclopentadienyl halide to the methyl group in the methylating agent is in the range of 1:3.3, 1:3.4, 1:3.5, 1:3.6, or any two of these values.
In some embodiments, the step of reacting the cyclopentadienyl platinum halide with a methylating agent comprises: firstly, adding a methylation reagent into cyclopentadienyl platinum halide at the temperature of 0-25 ℃, and then reacting for 12-24 h at the temperature of 10-30 ℃. In a specific example, during the addition of the methylating agent to the cyclopentadienyl platinum halide, the methylating agent is dissolved in an organic solvent such as diethyl ether and toluene, and added dropwise.
Further, in some embodiments, the step of reacting the cyclopentadienyl platinum halide with a methylating agent is followed by a purification step. Specifically, the purification step comprises:
adding a quenching agent into the system after the reaction, then removing the solvent to obtain a mixture of the trimethyl cyclopentadienyl platinum and the halide, and then removing the halide to obtain the trimethyl cyclopentadienyl platinum.
In one particular example, the quenching agent is water.
In one specific example, during halide removal, an organic solvent such as methylene chloride is added to the mixture, and a layer of diatomaceous earth is filtered to remove the halide.
Specifically, the chemical formula of trimethylcyclopentadienylplatinum is CpPtMe 3 Me is methyl and has the structural formula
. Reacting cyclopentadienyl platinum halide with a methylating agent to prepare trimethyl cyclopentadienyl platinum according to the reaction formula: CpPtX 3 +3CH 3 Li→CpPtMe 3 +3 LiX; alternatively, CpPtX 3 +Al(CH 3 ) 3 →CpPtMe 3 +AlX 3 . X is halogen.
Step S130: under the existence of Lewis acid, trimethyl cyclopentadienyl platinum and alkyl halide are subjected to Friedel-crafts reaction to prepare a platinum precursor.
Specifically, the alkyl halide is methyl halide. In a specific example, the alkyl halide is selected from at least one of methyl bromide and methyl iodide. The platinum precursor is trimethyl (methylcyclopentadienyl) platinum (IV). Experiments have shown that methyl iodide and methyl bromide have little difference in their effects during the preparation of trimethyl (methylcyclopentadienyl) platinum (IV), but methyl iodide is highly toxic, and therefore methyl bromide is preferred as the alkyl halide in this embodiment.
In some embodiments, the lewis acid is selected from at least one of aluminum trichloride, iron trichloride, tin tetrachloride, and zinc chloride.
In some embodiments, the molar ratio of trimethylcyclopentadienylplatinum to the Lewis acid and the alkyl halide is 1 (0.1-0.5) to 1.5-2.
In some embodiments, the step of friedel-crafts reacting trimethylcyclopentadienylplatinum with an alkyl halide comprises: adding trimethyl cyclopentadienyl platinum into a mixed system of Lewis acid and alkyl halide at the temperature of 0-30 ℃, and then reacting for 12-24 h at the temperature of 10-30 ℃. In a specific example, during the process of adding the trimethylcyclopentadienyl platinum to the mixed system of the lewis acid and the alkyl halide, the trimethylcyclopentadienyl platinum is dissolved in an organic solvent such as dichloromethane, tetrahydrofuran, and the like, and is added dropwise.
Further, in some embodiments, the friedel-crafts reaction of trimethylcyclopentadienylplatinum with an alkyl halide further comprises:
adding a quenching agent into the system after the Friedel-crafts reaction, and then passing through a silica gel column, removing a solvent, and sublimating and purifying.
In one particular example, the quenching agent is water.
In a specific example, the pressure during sublimation purification is 10Pa and the temperature is 35 ℃.
In the preparation process of the platinum precursor, a section of silica gel column is flushed during purification, which is beneficial to removing large-polarity impurities and some inorganic salts, and is beneficial to improving the product quality and the yield.
Specifically, the chemical formula of the platinum precursor is RCpPtMe 3 Structural formula is
. Performing Friedel-crafts reaction on trimethylcyclopentadienyl platinum and alkyl halide to prepare a platinum precursor according to the following reaction formula: CpPtMe 3 +RX→RCpPtMe 3 + HX, R is alkyl and X is halogen.
In one specific example, RX is MeX and the platinum precursor is mecppptme 3 Structural formula is
。
The preparation method of the platinum precursor has at least the following advantages:
(1) the preparation method of the platinum precursor takes platinum halide as a raw material, and the platinum halide reacts with cyclopentadienyl alkali metal salt under a protective atmosphere to obtain cyclopentadienyl platinum halide; then reacting with a methylating agent to generate trimethyl cyclopentadienyl platinum; finally, under the action of Lewis acid, the platinum precursor is subjected to Friedel-crafts reaction with alkyl halide to prepare a platinum precursor, and when the alkyl halide is methyl halide, a target product trimethyl (methyl cyclopentadienyl) platinum (IV) can be obtained. The method has simple process, high material activity in each step of reaction, no need of large excess of methylating reagent, and reduced complex dangerous operations caused by preparation of trimethyl platinum iodide, improved safety coefficient of reaction, and possibility of industrial production.
(2) The preparation method of the platinum precursor reduces the problem of a large amount of three wastes generated by preparing trimethyl platinum iodide, and simultaneously saves the cost.
(3) According to the preparation method of the platinum precursor, the trimethyl cyclopentadienyl platinum is prepared firstly, and then trimethyl (methyl cyclopentadienyl) platinum (IV) is prepared on the basis of the trimethyl cyclopentadienyl platinum, so that the operation is simple, the obtained product has high purity, and the trimethyl cyclopentadienyl platinum can be co-produced.
(4) The preparation method of the platinum precursor removes most of the impurity metals by using the adsorption silica gel, and then carries out sublimation purification, so that the purification efficiency is high and the impurity content is low.
(5) The preparation method of the platinum precursor has high yield which is more than 70 percent and even up to 90 percent.
The present invention also provides a method for preparing a metal thin film according to an embodiment, including the steps of:
step S210: and preparing a platinum precursor.
Specifically, the platinum precursor is prepared by the method for preparing a platinum precursor according to the above embodiment, which is not described herein again.
Step S220: the platinum precursor is decomposed to form a film on the substrate.
Specifically, the platinum precursor may be decomposed by thermal, chemical, photochemical or plasma-activated means.
In order to make the objects and advantages of the present invention more apparent, the following method for preparing a platinum precursor and the effects thereof will be described in further detail with reference to specific examples, it being understood that the specific examples are illustrative only and are not intended to limit the present invention. The following examples are not specifically described, and other components except inevitable impurities are not included. The examples, which are not specifically illustrated, employ drugs and equipment, all of which are conventional in the art. The experimental procedures, in which specific conditions are not indicated in the examples, were carried out according to conventional conditions, such as those described in the literature, in books, or as recommended by the manufacturer.
Example 1
The embodiment provides a preparation method of a platinum precursor, which comprises the following steps:
(1) under argon atmosphere, 33.7g of platinum (IV) chloride and 337mL of tetrahydrofuran were added to a 2L three-necked flask, the mixture was cooled to-10 ℃, 110mL of a 1.0M solution of cyclopentadienyl lithium in tetrahydrofuran was added dropwise thereto, the mixture was gradually dissolved in a reddish brown turbid solution, and the reaction was continued at this temperature for 30 minutes.
(2) The temperature is raised to 0 ℃, 206mL of 1.6M methyl lithium ether solution is added dropwise, the reaction solution becomes brown turbid solution, and the reaction is carried out for 12h at room temperature. And cooling to 0 ℃ again, dropwise adding 5mL of water for quenching, and evaporating the solvent under reduced pressure to obtain trimethylcyclopentadienyl platinum and a by-product lithium chloride. To the resulting product was added 200mL of dichloromethane, a layer of celite was filtered to remove lithium chloride, and a dark brown solution was obtained as a solution of trimethylcyclopentadienylplatinum in dichloromethane.
(3) And (3) adding 1.33g of anhydrous aluminum trichloride and 14.2g of methyl bromide into another 1L three-necked bottle, cooling to 0 ℃, dropwise adding the dichloromethane solution of the trimethylcyclopentadienyl platinum prepared in the step (2), returning to the room temperature after the addition is finished, and stirring for 12 hours to finish alkylation. Then 50mL of water is added dropwise for quenching, liquid separation is carried out, the organic phase is dried by anhydrous sodium sulfate, then a section of silica gel column with the thickness of 3cm is flushed, the solvent is evaporated by reduced pressure, the obtained brown crude product is transferred to a 250mL sublimer, and oil pump 10Pa is carried out at the temperature of 35 ℃ to sublimate light yellow crystals, namely trimethyl (methyl cyclopentadienyl) platinum of the embodiment. The mass of the obtained pale yellow crystals was 23.0g, and the yield was 72%.
Preparation of trimethyl (methylcyclopentadienyl) platinum prepared in this example 1 HNMR and 13 CNMR is shown in FIG. 1 and FIG. 2, respectively, and the deuterated reagent is CDCl 3 。
Example 2
The embodiment provides a preparation method of a platinum precursor, which comprises the following steps:
(1) under argon atmosphere, 33.7g of platinum (IV) chloride and 337mL of tetrahydrofuran were added to a 2L three-necked flask, the mixture was cooled to-10 ℃, 110mL of a 1.0M solution of cyclopentadienyl sodium in tetrahydrofuran was added dropwise thereto, the mixture was gradually dissolved in a reddish brown turbid solution, and the reaction was continued at this temperature for 30 minutes.
(2) The temperature is raised to 0 ℃, 206mL of 1.6M methyl lithium ether solution is added dropwise, the reaction solution becomes a brown turbid solution, and the reaction is carried out for 12h at room temperature. And cooling to 0 ℃ again, dropwise adding 5mL of water for quenching, and evaporating the solvent under reduced pressure to obtain the trimethylcyclopentadienyl platinum and the byproduct sodium chloride. To the resulting product was added 200mL of dichloromethane, a layer of celite was filtered to remove the sodium chloride and a dark brown solution was obtained as a solution of trimethylcyclopentadienylplatinum in dichloromethane.
(3) And (3) adding 1.33g of anhydrous aluminum trichloride and 14.2g of methyl bromide into another 1L three-mouth bottle, cooling to 0 ℃, dropwise adding the dichloromethane solution of the trimethylcyclopentadienyl platinum prepared in the step (2), returning to the room temperature after the addition is finished, and stirring for 12 hours to finish alkylation. 50mL of water is added dropwise for quenching, liquid separation is carried out, the organic phase is dried by anhydrous sodium sulfate, then a section of silica gel column with the thickness of 3cm is washed, the solvent is evaporated by decompression, the obtained dark brown crude product is transferred to a 250mL sublimator, an oil pump is arranged at 10Pa, the temperature is 35 ℃, and yellow crystals, namely trimethyl (methyl cyclopentadienyl) platinum in the embodiment, are sublimed. The obtained yellow crystals had a mass of 23.8g and a yield of 74.5%.
Preparation of trimethyl (methylcyclopentadienyl) platinum prepared in this example 1 HNMR and 13 CNMR is shown in FIG. 3 and FIG. 4, respectively, and the deuterated reagent is CDCl 3 。
Example 3
The embodiment provides a preparation method of a platinum precursor, which includes the following steps:
(1) under argon atmosphere, 33.7g of platinum (IV) chloride and 337mL of tetrahydrofuran were added to a 2L three-necked flask, the mixture was cooled to-10 ℃, 110mL of a 1.0M solution of cyclopentadienyl potassium in tetrahydrofuran was added dropwise thereto, the mixture was gradually dissolved in a reddish brown turbid solution, and the reaction was continued at this temperature for 30 minutes.
(2) The temperature is raised to 0 ℃, 206mL of 1.6M methyl lithium ether solution is added dropwise, the reaction solution becomes a brown turbid solution, and the reaction is carried out for 12h at room temperature. And cooling to 0 ℃ again, dropwise adding 5mL of water for quenching, and evaporating the solvent under reduced pressure to obtain the trimethylcyclopentadienyl platinum and the byproduct potassium chloride. To the resulting product was added 200mL of dichloromethane, a layer of celite was filtered to remove the potassium chloride and a dark brown solution was obtained as a solution of trimethylcyclopentadienylplatinum in dichloromethane.
(3) And (3) adding 1.33g of anhydrous aluminum trichloride and 14.2g of methyl bromide into another 1L three-mouth bottle, cooling to 0 ℃, dropwise adding the dichloromethane solution of the trimethylcyclopentadienyl platinum prepared in the step (2), returning to the room temperature after the addition is finished, and stirring for 12 hours to finish alkylation. Then 50mL of water is added dropwise for quenching, liquid separation is carried out, the organic phase is dried by anhydrous sodium sulfate, then a section of silica gel column with the thickness of 3cm is flushed, the solvent is evaporated by reduced pressure, the obtained dark brown crude product is transferred to a 250mL sublimer, an oil pump is arranged at 10Pa, the temperature is 35 ℃, and yellow crystals, namely trimethyl (methyl cyclopentadienyl) platinum of the embodiment, are sublimed. The mass of the obtained yellow crystals was 23.6g, and the yield was 73.9%.
Preparation of trimethyl (methylcyclopentadienyl) platinum prepared in this example 1 HNMR and 13 CNMR is shown in FIG. 5 and FIG. 6, respectively, and the deuterated reagent used is CDCl 3 。
Example 4
The embodiment provides a preparation method of a platinum precursor, which includes the following steps:
(1) under argon atmosphere, 33.7g of platinum (IV) chloride and 337mL of tetrahydrofuran were added to a 2L three-necked flask, the mixture was cooled to-10 ℃, 110mL of a 1.0M solution of cyclopentadienyl lithium in tetrahydrofuran was added dropwise thereto, the mixture was gradually dissolved in a reddish brown turbid solution, and the reaction was continued at this temperature for 30 minutes.
(2) The temperature is increased to 0 ℃, 120mL of 1.0M trimethylaluminum toluene solution is added dropwise, the reaction solution becomes a brown turbid solution, and the reaction is carried out for 12h at room temperature. And cooling to 0 ℃ again, dropwise adding 5mL of water for quenching, and evaporating the solvent under reduced pressure to obtain trimethylcyclopentadienyl platinum and a byproduct aluminum chloride. To the resulting product was added 200mL of dichloromethane, a layer of celite was filtered to remove aluminum chloride, and a brown-yellow solution, i.e., a solution of trimethylcyclopentadienylplatinum in dichloromethane, was obtained.
(3) And (3) adding 1.33g of anhydrous aluminum trichloride and 14.2g of methyl bromide into another 1L three-necked bottle, cooling to 0 ℃, dropwise adding the dichloromethane solution of the trimethylcyclopentadienyl platinum prepared in the step (2), returning to the room temperature after the addition is finished, and stirring for 12 hours to finish alkylation. Then 50mL of water is added dropwise for quenching, liquid separation is carried out, the organic phase is dried by anhydrous sodium sulfate, then a section of silica gel column with the thickness of 3cm is washed, the solvent is evaporated by decompression, the obtained brown crude product is transferred to a 250mL sublimer, an oil pump is carried out at 10Pa, the temperature is 35 ℃, and white crystals, namely trimethyl (methyl cyclopentadienyl) platinum of the embodiment, are sublimated. The obtained white crystals had a mass of 28.8g and a yield of 90.3%.
Preparation of trimethyl (methylcyclopentadienyl) platinum prepared in this example 1 HNMR and 13 CNMR is shown in FIG. 7 and FIG. 8, respectively, and the deuterated reagent used is CDCl 3 。
Example 5
The embodiment provides a preparation method of a platinum precursor, which comprises the following steps:
(1) under argon atmosphere, 33.7g of platinum (IV) chloride and 337mL of tetrahydrofuran were added to a 2L three-necked flask, the mixture was cooled to-10 ℃, 110mL of a 1.0M solution of cyclopentadienyl lithium in tetrahydrofuran was added dropwise thereto, the mixture was gradually dissolved in a reddish brown turbid solution, and the reaction was continued at this temperature for 30 minutes.
(2) The temperature is increased to 0 ℃, 120mL of 1.0M trimethylaluminum toluene solution is added dropwise, the reaction solution becomes a brown turbid solution, and the reaction is carried out for 12h at room temperature. And cooling to 0 ℃ again, dropwise adding 5mL of water for quenching, and evaporating the solvent under reduced pressure to obtain trimethylcyclopentadienyl platinum and a byproduct aluminum chloride. To the resulting product was added 200mL of dichloromethane, a layer of celite was filtered to remove aluminum chloride, and a tan solution, i.e., a dichloromethane solution of trimethylcyclopentadienyl platinum, was obtained.
(3) And (3) adding 1.33g of anhydrous aluminum trichloride and 21.3g of methyl iodide into another 1L three-mouth bottle, cooling to 0 ℃, dropwise adding the dichloromethane solution of the trimethylcyclopentadienyl platinum prepared in the step (2), returning to the room temperature after the addition is finished, and stirring for 12 hours to finish alkylation. Then 50mL of water is added dropwise for quenching, liquid separation is carried out, the organic phase is dried by anhydrous sodium sulfate, then a section of silica gel column with the thickness of 3cm is flushed, the solvent is evaporated by reduced pressure, the obtained brown crude product is transferred to a 250mL sublimer, and white crystals, namely trimethyl (methylcyclopentadienyl) platinum in the embodiment, are sublimated at the temperature of 35 ℃ under the oil pump 10 Pa. The mass of the obtained white crystals was 27.6g, and the yield was 86.5%.
Preparation of trimethyl (methylcyclopentadienyl) platinum prepared in this example 1 HNMR and 13 CNMR is shown in FIG. 9 and FIG. 10, respectively, and the deuterated reagent used is CDCl 3 。
As can be seen from a comparison of example 4 and example 5, methyl iodide is less effective than methyl bromide in the preparation of trimethyl (methylcyclopentadienyl) platinum (IV), but methyl iodide is more toxic, so methyl bromide is preferred.
Example 6
The embodiment provides a preparation method of a platinum precursor, which comprises the following steps:
(1) under argon atmosphere, 33.7g of platinum (IV) chloride and 337mL of tetrahydrofuran were added to a 2L three-necked flask, the mixture was cooled to-10 ℃, 110mL of a 1.0M solution of cyclopentadienyl lithium in tetrahydrofuran was added dropwise thereto, the mixture was gradually dissolved in a reddish brown turbid solution, and the reaction was continued at this temperature for 30 minutes.
(2) The temperature is increased to 0 ℃, 120mL of 1.0M trimethylaluminum toluene solution is added dropwise, the reaction solution becomes a brown turbid solution, and the reaction is carried out for 12h at room temperature. And cooling to 0 ℃ again, dropwise adding 5mL of water for quenching, and evaporating the solvent under reduced pressure to obtain trimethylcyclopentadienyl platinum and a byproduct aluminum chloride. To the resulting product was added 200mL of dichloromethane, a layer of celite was filtered to remove aluminum chloride, and a brown-yellow solution, i.e., a solution of trimethylcyclopentadienylplatinum in dichloromethane, was obtained.
(3) And (3) adding 1.33g of anhydrous aluminum trichloride and 14.2g of methyl bromide into another 1L three-necked bottle, cooling to 0 ℃, dropwise adding the dichloromethane solution of the trimethylcyclopentadienyl platinum prepared in the step (2), returning to the room temperature after the addition is finished, and stirring for 12 hours to finish alkylation. Quenching by dropping 50mL of water, separating, drying the organic phase with anhydrous sodium sulfate, evaporating the solvent under reduced pressure, transferring the obtained brown crude product to a 250mL sublimator, pumping 10Pa oil, sublimating at 35 ℃ to obtain brown crystals, namely trimethyl (methylcyclopentadienyl) platinum of the embodiment. The mass of the resulting brown crystals was 26.2g, and the yield was 82.2%.
As can be seen from the comparison between example 4 and example 6, in the preparation process of trimethyl (methylcyclopentadienyl) platinum (IV), a silica gel column is flushed during purification, which is helpful for removing the large polar impurities and some inorganic salts, and is beneficial for improving the product quality and increasing the yield.
Comparative example 1
Comparative example 1 provides a method for preparing a platinum precursor, comprising the steps of:
under the condition of argon, 33.7g of platinum (IV) chloride and 337mL of tetrahydrofuran are added into a 2L three-necked bottle, the mixture is cooled to-10 ℃, 110mL of 1.5M tetrahydrofuran solution of cyclopentadienyl trimethyl silicon is dropwise added, and no obvious phenomenon change is found in the red-brown turbid liquid after 2 hours. Presumably, the cyclopentadienyl trimethylsilane activity was insufficient and further charging was abandoned.
As can be seen from the comparison of examples 1 to 3 with comparative example 1, in the preparation of cyclopentadienylplatinum chloride, cyclopentadienyl lithium, cyclopentadienyl sodium and cyclopentadienyl potassium were all almost as good from the viewpoint of yield, while cyclopentadienyl trimethyl silicon was not sufficiently active to be hardly reacted. The cyclopentadienyl sodium and the cyclopentadienyl potassium have strong alkalinity, so that the final product has dark color. In addition, in view of ease of preparation, cyclopentadienyl lithium is preferably selected.
Comparative example 2
Comparative example 2 provides a method for preparing a platinum precursor, comprising the steps of:
(1) under argon atmosphere, 33.7g of platinum (IV) chloride and 337mL of tetrahydrofuran were added to a 2L three-necked flask, the mixture was cooled to-10 ℃, 110mL of a 1.0M solution of cyclopentadienyl lithium in tetrahydrofuran was added dropwise thereto, the mixture was gradually dissolved in a reddish brown turbid solution, and the reaction was continued at this temperature for 30 minutes.
(2) The temperature is raised to 0 ℃, 120mL of 3.0M methyl magnesium bromide in ether solution is added dropwise, the reaction solution becomes a brown turbid solution, and the reaction is carried out for 12h at room temperature. And cooling to 0 ℃ again, dropwise adding 5mL of water for quenching, and evaporating the solvent under reduced pressure to obtain trimethylcyclopentadienyl platinum and a by-product magnesium chloride. To the resulting product was added 200mL of dichloromethane, and a layer of celite was filtered to remove the magnesium chloride, yielding a pale yellow solution, i.e., a dichloromethane solution of trimethylcyclopentadienylplatinum.
(3) And (3) adding 1.33g of anhydrous aluminum trichloride and 14.2g of methyl bromide into another 1L three-mouth bottle, cooling to 0 ℃, dropwise adding the dichloromethane solution of the trimethylcyclopentadienyl platinum prepared in the step (2), returning to the room temperature after the addition is finished, and stirring for 12 hours to finish alkylation. Quenching is carried out by adding 50mL of water, separating liquid, drying an organic phase by anhydrous sodium sulfate, washing a section of silica gel column with the thickness of 3cm, reducing pressure, drying the solvent, transferring the obtained brown sticky substance into a 250mL sublimator, arranging an oil pump with the pressure of 10Pa, and heating to 50 ℃ at the temperature of 35 ℃ without sublimating the product.
As can be seen from a comparison of example 1, example 4 and comparative example 2, methyl magnesium bromide is less active than the methyl lithium reagent and the trimethyl aluminum reagent in the preparation of trimethyl cyclopentadienyl platinum. The yield and appearance of the product prepared from trimethylaluminum are relatively good.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, so as to understand the technical solutions of the present invention specifically and in detail, but not to be understood as the limitation of the protection scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. It should be understood that the technical solutions provided by the present invention, which are obtained by logical analysis, reasoning or limited experiments, are within the scope of the appended claims. Therefore, the protection scope of the present invention should be subject to the content of the appended claims, and the description and the drawings can be used for explaining the content of the claims.
Claims (10)
1. A preparation method of a platinum precursor is characterized by comprising the following steps:
reacting platinum halide with cyclopentadienyl alkali metal salt in a protective atmosphere to prepare cyclopentadienyl platinum halide;
reacting the cyclopentadienyl platinum halide with a methylating agent to prepare trimethyl cyclopentadienyl platinum; and
and carrying out Friedel-crafts reaction on the trimethylcyclopentadienyl platinum and the alkyl halide in the presence of Lewis acid to prepare a platinum precursor.
2. The method for producing a platinum precursor according to claim 1, wherein the cyclopentadienyl alkali metal salt is at least one member selected from the group consisting of cyclopentadienyl lithium, cyclopentadienyl sodium and cyclopentadienyl potassium; and/or the like, and/or,
the platinum halide is platinum tetrachloride.
3. The method of preparing a platinum precursor according to claim 1, wherein the methylating agent is at least one selected from the group consisting of methyllithium and trimethylaluminum.
4. The method of preparing a platinum precursor according to claim 1, wherein the alkyl halide is at least one selected from the group consisting of methyl bromide and methyl iodide, and the platinum precursor is trimethyl (methylcyclopentadienyl) platinum.
5. The method for producing a platinum precursor according to claim 1, further comprising, after the step of subjecting the trimethylcyclopentadienylplatinum to a friedel-crafts reaction with an alkyl halide:
adding a quenching agent into the system after the Friedel-crafts reaction to quench the reaction, and then passing through a silica gel column, removing the solvent, and sublimating and purifying.
6. The method for producing a platinum precursor according to any one of claims 1 to 5, wherein the molar ratio of the platinum halide to the cyclopentadienyl alkali metal salt is 1 (1.1 to 1.5); and/or the presence of a catalyst in the reaction mixture,
in the step of reacting the platinum halide with the cyclopentadienyl alkali metal salt, the reaction temperature is-10 ℃ to 0 ℃, and the reaction time is 30min to 120 min.
7. The method for producing a platinum precursor according to any one of claims 1 to 5, wherein the molar ratio of the cyclopentadienyl platinum halide to the methyl group in the methylating agent is 1 (3.3 to 3.6); and/or the presence of a catalyst in the reaction mixture,
the step of reacting the cyclopentadienyl platinum halide with a methylating agent comprises: the methylation reagent is added into the cyclopentadienyl platinum halide at the temperature of 0-25 ℃, and then the reaction is carried out for 12-24 h at the temperature of 10-30 ℃.
8. The method for preparing a platinum precursor according to any one of claims 1 to 5, wherein the molar ratio of the trimethylcyclopentadienyl platinum to the Lewis acid and the alkyl halide is 1 (0.1 to 0.5) to 1.5 to 2; and/or the presence of a catalyst in the reaction mixture,
the Friedel-crafts reaction of the trimethylcyclopentadienyl platinum and the alkyl halide comprises the following steps: adding the trimethylcyclopentadienyl platinum into the mixed system of the Lewis acid and the alkyl halide at the temperature of 0-30 ℃, and then reacting for 12-24 h at the temperature of 10-30 ℃; and/or the like, and/or,
the Lewis acid is at least one selected from aluminum trichloride, ferric trichloride, stannic chloride and zinc chloride.
9. A preparation method of trimethyl cyclopentadienyl platinum is characterized by comprising the following steps:
reacting platinum halide with cyclopentadienyl alkali metal salt in a protective atmosphere to prepare cyclopentadienyl platinum halide; and
and reacting the cyclopentadienyl platinum halide with a methylating agent to prepare trimethyl cyclopentadienyl platinum.
10. The preparation method of the metal film is characterized by comprising the following steps:
preparing a platinum precursor by the preparation method of any one of claims 1 to 8; and
the platinum precursor is decomposed to form a film on the substrate.
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| US20040010158A1 (en) * | 2002-06-12 | 2004-01-15 | Meiere Scott Houston | Method for producing organometallic compounds |
| CN101925608A (en) * | 2008-01-25 | 2010-12-22 | 瓦克化学股份公司 | Hydrosilylation reactions activated through radiation |
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|---|---|---|---|---|
| US20040010158A1 (en) * | 2002-06-12 | 2004-01-15 | Meiere Scott Houston | Method for producing organometallic compounds |
| CN101925608A (en) * | 2008-01-25 | 2010-12-22 | 瓦克化学股份公司 | Hydrosilylation reactions activated through radiation |
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| ALAN SHAVER: "Preparation of some cyclopentadienyl platinum (IV) complexes", 《CANADIAN JOURNAL OF CHEMISTRY》 * |
| LARRY D. BOARDMAN等: "195Pt NMR Study of (η5-Cyclopentadienyl) trialkylplatinum(IV) Cornplexes", 《MAGNETIC RESONANCE IN CHEMISTRY》 * |
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