CN1617948A - 用于通过原子层沉积来沉积铜膜的挥发性铜(ii)配合物 - Google Patents
用于通过原子层沉积来沉积铜膜的挥发性铜(ii)配合物 Download PDFInfo
- Publication number
- CN1617948A CN1617948A CNA038023024A CN03802302A CN1617948A CN 1617948 A CN1617948 A CN 1617948A CN A038023024 A CNA038023024 A CN A038023024A CN 03802302 A CN03802302 A CN 03802302A CN 1617948 A CN1617948 A CN 1617948A
- Authority
- CN
- China
- Prior art keywords
- copper
- alkyl
- methyl
- pyridyl
- base material
- 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.)
- Granted
Links
- 239000010949 copper Substances 0.000 title claims abstract description 39
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 38
- 238000000151 deposition Methods 0.000 title abstract description 12
- 238000000231 atomic layer deposition Methods 0.000 title abstract description 4
- 230000008021 deposition Effects 0.000 title abstract description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical class [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 title description 18
- 238000000034 method Methods 0.000 claims abstract description 48
- 229910000071 diazene Inorganic materials 0.000 claims abstract description 21
- 230000008569 process Effects 0.000 claims abstract description 15
- 229910052799 carbon Inorganic materials 0.000 claims description 46
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 42
- -1 amine salt Chemical class 0.000 claims description 34
- 150000004699 copper complex Chemical class 0.000 claims description 31
- 229910052739 hydrogen Inorganic materials 0.000 claims description 31
- 239000000463 material Substances 0.000 claims description 29
- 230000002829 reductive effect Effects 0.000 claims description 24
- 125000000339 4-pyridyl group Chemical group N1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 claims description 23
- 239000003795 chemical substances by application Substances 0.000 claims description 22
- 239000003153 chemical reaction reagent Substances 0.000 claims description 19
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims description 17
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 230000002152 alkylating effect Effects 0.000 claims description 11
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 10
- UCXUKTLCVSGCNR-UHFFFAOYSA-N diethylsilane Chemical compound CC[SiH2]CC UCXUKTLCVSGCNR-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 8
- 230000004888 barrier function Effects 0.000 claims description 7
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 6
- 229910000077 silane Inorganic materials 0.000 claims description 6
- 229960001866 silicon dioxide Drugs 0.000 claims description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- AMKGKYQBASDDJB-UHFFFAOYSA-N 9$l^{2}-borabicyclo[3.3.1]nonane Chemical group C1CCC2CCCC1[B]2 AMKGKYQBASDDJB-UHFFFAOYSA-N 0.000 claims description 5
- FEJUGLKDZJDVFY-UHFFFAOYSA-N 9-borabicyclo[3.3.1]nonane Substances C1CCC2CCCC1B2 FEJUGLKDZJDVFY-UHFFFAOYSA-N 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 229910000085 borane Inorganic materials 0.000 claims description 5
- 150000002576 ketones Chemical class 0.000 claims description 5
- DNXIASIHZYFFRO-UHFFFAOYSA-N pyrazoline Chemical compound C1CN=NC1 DNXIASIHZYFFRO-UHFFFAOYSA-N 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 5
- 150000003973 alkyl amines Chemical class 0.000 claims description 4
- UBHZUDXTHNMNLD-UHFFFAOYSA-N dimethylsilane Chemical compound C[SiH2]C UBHZUDXTHNMNLD-UHFFFAOYSA-N 0.000 claims description 4
- KCWYOFZQRFCIIE-UHFFFAOYSA-N ethylsilane Chemical compound CC[SiH3] KCWYOFZQRFCIIE-UHFFFAOYSA-N 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000005527 methyl sulfate group Chemical group 0.000 claims description 4
- PARWUHTVGZSQPD-UHFFFAOYSA-N phenylsilane Chemical compound [SiH3]C1=CC=CC=C1 PARWUHTVGZSQPD-UHFFFAOYSA-N 0.000 claims description 4
- KIWBPDUYBMNFTB-UHFFFAOYSA-N Ethyl hydrogen sulfate Chemical compound CCOS(O)(=O)=O KIWBPDUYBMNFTB-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims description 3
- VQYPKWOGIPDGPN-UHFFFAOYSA-N [C].[Ta] Chemical compound [C].[Ta] VQYPKWOGIPDGPN-UHFFFAOYSA-N 0.000 claims description 3
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 claims description 3
- CFJRGWXELQQLSA-UHFFFAOYSA-N azanylidyneniobium Chemical compound [Nb]#N CFJRGWXELQQLSA-UHFFFAOYSA-N 0.000 claims description 3
- XDRMBCMMABGNMM-UHFFFAOYSA-N ethyl benzenesulfonate Chemical compound CCOS(=O)(=O)C1=CC=CC=C1 XDRMBCMMABGNMM-UHFFFAOYSA-N 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- CZXGXYBOQYQXQD-UHFFFAOYSA-N methyl benzenesulfonate Chemical compound COS(=O)(=O)C1=CC=CC=C1 CZXGXYBOQYQXQD-UHFFFAOYSA-N 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 3
- HWEYZGSCHQNNEH-UHFFFAOYSA-N silicon tantalum Chemical compound [Si].[Ta] HWEYZGSCHQNNEH-UHFFFAOYSA-N 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical group [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 3
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical class N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 claims description 2
- UIUXUFNYAYAMOE-UHFFFAOYSA-N methylsilane Chemical compound [SiH3]C UIUXUFNYAYAMOE-UHFFFAOYSA-N 0.000 claims description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 1
- 239000007787 solid Substances 0.000 abstract description 9
- 239000000758 substrate Substances 0.000 abstract description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 22
- 238000002360 preparation method Methods 0.000 description 19
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 15
- 239000002585 base Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000010408 film Substances 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 239000003446 ligand Substances 0.000 description 9
- 230000009467 reduction Effects 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 238000004821 distillation Methods 0.000 description 6
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 238000005229 chemical vapour deposition Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 238000005576 amination reaction Methods 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000010926 purge Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000012691 Cu precursor Substances 0.000 description 3
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000002168 alkylating agent Substances 0.000 description 2
- 229940100198 alkylating agent Drugs 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- AIJULSRZWUXGPQ-UHFFFAOYSA-N Methylglyoxal Chemical compound CC(=O)C=O AIJULSRZWUXGPQ-UHFFFAOYSA-N 0.000 description 1
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- JRBRVDCKNXZZGH-UHFFFAOYSA-N alumane;copper Chemical compound [AlH3].[Cu] JRBRVDCKNXZZGH-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- ZQDLJYBJPOGCHN-UHFFFAOYSA-N copper ethanol Chemical compound [Cu+2].C(C)O ZQDLJYBJPOGCHN-UHFFFAOYSA-N 0.000 description 1
- SCGJLFGXXZTXSX-UHFFFAOYSA-N copper;ethanol Chemical compound [Cu].CCO SCGJLFGXXZTXSX-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 150000007857 hydrazones Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000002466 imines Chemical group 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- DWCSXQCXXITVKE-UHFFFAOYSA-N triethyloxidanium Chemical class CC[O+](CC)CC DWCSXQCXXITVKE-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45553—Atomic layer deposition [ALD] characterized by the use of precursors specially adapted for ALD
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
- C07C251/04—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C251/10—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of an unsaturated carbon skeleton
- C07C251/12—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of an unsaturated carbon skeleton being acyclic
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
- C07C251/04—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C251/10—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of an unsaturated carbon skeleton
- C07C251/16—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of an unsaturated carbon skeleton containing six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/72—Nitrogen atoms
- C07D213/74—Amino or imino radicals substituted by hydrocarbon or substituted hydrocarbon radicals
-
- 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]
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
- H01L21/288—Deposition of conductive or insulating materials for electrodes conducting electric current from a liquid, e.g. electrolytic deposition
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- H—ELECTRICITY
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Abstract
本发明涉及新的1,3-二亚胺铜配合物以及1,3-二亚胺铜配合物用于在原子层沉积法中在基材上沉积铜或在多孔固体之中或之上沉积铜的用途。本发明还提供一种生产氨基亚胺的方法以及新的氨基亚胺化合物。
Description
发明领域
本发明涉及新的1,3-二亚胺铜配合物以及1,3-二亚胺铜配合物用于在原子层沉积法中在基材上沉积铜或在多孔固体之中或之上沉积铜的用途。本发明还提供一种生产氨基亚胺的方法以及新的氨基亚胺化合物。
技术背景
ALD(原子层沉积)方法用于形成薄膜,如M.Ritala和M.Leskela在Handbook of Thin Film Materials中的“Atomic LayerDeposition”所述(H.S.Nalwa编辑,Academic Press,San Diego,2001,第1卷,第2章)。这些膜,特别是金属和金属氧化物膜,是在生产电路和电子设备中的关键组分。
在用于沉积铜膜的ALD法中,铜前体和还原剂被交替地引入反应室中。在铜前体被引入反应室中并被吸收在基材上之后,过量的(未吸收的)前体蒸气从该反应室中泵出或吹扫出来。然后,引入能与铜前体反应形成铜金属和游离形式配体的还原剂。这种循环可以在需要时重复进行以达到所需的膜厚度。
该方法与化学气相沉积(CVD)的区别在于金属配合物的沉积化学机理。在CVD方法中,配合物在与表面接触时分解,得到所需的膜。在ALD方法中,配合物在与表面接触时不会分解。而膜的形成是在引入第二种试剂时发生,该试剂能与沉积的金属配合物反应。在由铜(II)配合物制备铜膜的过程中,第二种试剂是还原剂。
为了用于ALD方法,铜配合物必须具有足够的挥发性以便在没有热分解的情况下升华。一般,含三氟甲基的配体已经用于提高铜配合物的挥发性。但是,这种方法在互联层的制备中有缺陷,因为卤化物不利地影响互联层的性能。
在ALD方法中使用的配体必须还对于分解是稳定的并能从配合物中以不含金属的形式解吸。在铜的还原之后,配体被释放出来并必须从表面上除去以防止它进入正在形成的金属层中。
US5464666描述了1,3-二亚胺铜配合物在氢气存在下分解形成铜。该专利还描述了1,3-二亚胺铜配合物在用于生产铜-铝合金的化学气相沉积法中的用途。
DE4202889描述了1,3-二亚胺金属配合物用于沉积涂层的用途,优选通过化学气相沉积法进行。公开了金属配合物在还原气氛、优选氢气中的分解。
S.G.McGeachin在Canadian Journal of Chemistry,46,1903-1912(1968)中描述了1,3-二亚胺以及这些配体的金属配合物的合成。
N.A.Domnin和S.I.Yakimovich,Zh.Organ.Khim,1965,1(4),658描述了脂族β-二酮与不对称N,N-二烷基肼反应形成双(二烷基腙)。
发明概述
本发明描述了-种在基材上形成铜沉积物的方法,包括:
a.使基材与铜配合物(I)接触,形成铜配合物在该基材上的沉积物;和
b.使沉积的铜配合物与还原剂接触,其中
R1和R4独立地选自H、C1-C5烷基和二甲基氨基;
R2和R3独立地选自H、C1-C5烷基、苯基、苄基和4-吡啶基,前提是在R1至R4中的碳总数是4-12;和
还原剂选自9-BBN、硼烷、二氢苯并呋喃、吡唑啉、二乙基硅烷、二甲基硅烷、乙基硅烷、甲基硅烷、苯基硅烷和硅烷。
在另一个实施方案中,本发明提供1,3-二亚胺铜配合物(II),
其中
R5和R8是二甲基氨基;和
R6和R7独立地选自H、C1-C5烷基、苯基、苄基和4-吡啶基,前提是在R5至R8中的碳总数是4-14;或
R5和R8独立地选自H、C1-C5烷基和二甲基氨基;和
R6和R7选自H、C1-C5烷基、苯基、苄基和4-吡啶基,前提是R6或R7是4-吡啶基,和前提是在R5至R8中的碳总数是4-14。
在另一个实施方案中,本发明提供含有沉积在基材上的1,3-二亚胺铜配合物(II)的制品。
在另一个实施方案中,本发明提供合成二亚胺化合物的方法,包括:
a.使烷基亚氨基-单酮(III)与烷基化剂接触,形成相应的O-烷基化衍生物(IV);
b.使步骤(a)的O-烷基化衍生物(IV)与伯烷基胺NH2R13接触,形成亚胺鎓盐(V);和
c.使步骤(b)的亚胺鎓盐(V)与强碱接触,形成相应的中性氨基亚胺(VI):
其中
R10和R11独立地选自H、C1-C5烷基、苯基、苄基和4-吡啶基;
R12是Me或Et;
R9和R13独立地选自H和C1-C5烷基,前提是在R9、R10、R11和R13中的碳总数是4-12;
烷基化试剂选自硫酸二甲酯、苯磺酸甲酯、甲苯磺酸甲酯、硫酸二乙酯、苯磺酸乙酯、三氟甲烷磺酸甲酯和甲苯磺酸乙酯;和
X-是衍生自烷基化试剂的阴离子。
在另一个实施方案中,本发明提供新的氨基亚胺化合物(VII)
其中
R14和R17独立地选自H、C1-C5烷基和二甲基氨基;和
R15和R16独立地选自H、C1-C5烷基、苯基、苄基和4-吡啶基,前提是R15或R16是4-吡啶基,和前提是在R14至R17中的碳总数是4-14。
发明详述
申请人已经发现适用于产生用作在形成集成电路的铜互联网中的种子层或用于装饰性应用或催化应用的原子层沉积(ALD)方法。该方法使用铜(II)配合物,它是挥发性的、热稳定的并衍生自仅含C、H和N的配体。选择这些配体以形成在适宜温度范围内是挥发性的但在该温度范围内不分解的铜(II)配合物;另外,这些配合物在添加合适的还原剂时分解成金属。进一步选择这些配体,使得它们在接触还原剂时不分解的情况下解吸。通过易得的还原剂将这些铜配合物还原成铜金属的过程已经证明可以完全在温和的温度下进行。
在本发明方法中,通过以下步骤将铜沉积在基材上:
a.使基材与铜配合物(I)接触,形成铜配合物在该基材上的沉积物;和
b.使沉积的铜配合物与还原剂接触,其中
R1和R4独立地选自H、C1-C5烷基和二甲基氨基;
R2和R3独立地选自H、C1-C5烷基、苯基、苄基和4-吡啶基,前提是在R1至R4中的碳总数是4-12;和
还原剂选自9-BBN、硼烷、二氢苯并呋喃、吡唑啉、二乙基硅烷、二甲基硅烷、乙基硅烷、苯基硅烷和硅烷。
通过允许在较低温下进行且制得更均匀的膜,本发明的沉积方法改进了现有技术中所述的方法。
在本发明的铜沉积方法中,铜可以沉积在基材的表面上、基材的孔隙之中或之上。合适基材包括铜、硅片、在生产超大规模集成电路中使用的芯片,用具有比二氧化硅更低的介电常数的介电材料制备的芯片、以及涂有阻隔层的二氧化硅和低k基材。用于防止铜迁移的阻隔层包括钽、氮化钽、钛、氮化钛、氮化硅钽、氮化硅钛、氮化碳钽和氮化铌。
该方法可以在溶液中进行,即通过使铜配合物的溶液与还原剂接触进行。但是,优选将基材暴露在铜配合物的蒸气中,然后在沉积的配合物与还原剂蒸气接触之前通过真空或吹扫除去任何多余的铜配合物(即未沉积的配合物)。在铜配合物还原之后,可以通过真空、吹扫、加热、用合适的溶剂洗涤或这些步骤的组合来除去游离形式的配体。
该方法重复进行,直到获得更厚的铜层或消除针孔。
铜配合物的沉积通常在0-120℃下进行。铜配合物的还原通常在相似的温度0-120℃下进行。
需要强还原剂来快速完全地还原铜配合物。还原剂必须是挥发性的,且在加热时不会分解。它们还必须具有足够的还原能力,从而在与沉积在铜表面上的铜配合物接触时能快速地反应。已经确定了一组合适的还原剂,它们以前未曾用于在ALD方法中铜(II)的还原。这些试剂的一个特征是存在质子给体。该试剂必须能转移至少一个电子以还原配合物的铜离子,并能转移至少一个质子以将配体质子化。被氧化的还原剂和被质子化的配体随后必须能容易地从新形成的铜沉积物表面上除去。
适用于本发明铜沉积方法的还原剂包括9-BBN、硼烷、二氢苯并呋喃、吡唑啉、二乙基硅烷、二甲基硅烷、乙基硅烷、苯基硅烷和硅烷。优选二乙基硅烷和硅烷。
在铜沉积方法的工业实施方案中,将铜配合物在温度、时间和压力条件下加入反应器中以实现配合物对基材表面的适当作用。本领域技术人员将能理解到这些参数的选择取决于各室和系统设计以及所要求的工艺速率。在沉积在基材上之后(例如涂覆的硅片),从室中泵出或吹扫出配合物蒸气,将还原剂在约50-760mTorr的压力下引入室中以便还原被吸收的铜配合物。在还原期间,将基材保持在约0-120℃的温度下。该反应必须是迅速且完全的。还原剂的暴露时间可以是从少于1秒到几分钟。该反应产物然后必须脱离表面。优选的试剂是铜1,3-二亚胺配合物(I,其中R1、R3和R4是Me,和R2是苯基)和二乙基硅烷。
在本发明的铜沉积方法中使用的铜(II)配合物分为两类:具有对称配体的那些(R1=R4和R2=R3)和具有不对称配体的那些(R1≠R4和/或R2≠R3)。具有对称配体的铜(II)配合物是显示良好挥发性和稳定性的固体。选自该组的优选配体是N,N’-二乙基衍生物,其中R1=R4=乙基,和R2=R3=甲基。但是,不对称配体倾向于得到挥发性更强的配合物,这是由更低的升华温度显示的。例如,对称的N,N’-二乙基衍生物可以在45-50℃在100mTorr压力下升华,而N-甲基-N’-乙基衍生物(R1=乙基,和R2=R3=R4=甲基)在约25℃在100mTorr下升华。不对称配合物可以在比衍生自对称配体的那些更低的操作温度下使用,有助于避免不利的反应例如铜配合物的分解。
在另一个实施方案中,本发明提供新的1,3-二亚胺铜配合物(II)
其中
R5和R8是二甲基氨基;和
R6和R7独立地选自H、C1-C5烷基、苯基、苄基和4-吡啶基,前提是在R5至R8中的碳总数是4-14;或
R5和R8独立地选自H、C1-C5烷基和二甲基氨基;和
R6和R7选自H、C1-C5烷基、苯基、苄基和4-吡啶基,前提是R6或R7是4-吡啶基,和前提是在R5至R8中的碳总数是4-14。
新的铜配合物(II)用于本发明的铜沉积方法中。优选的是,R5和R8是二甲基氨基,R6和R7是C1-C5烷基,前提是R5至R8中的碳总数是5-10。
在另一个实施方案中,本发明提供含有沉积在基材上的1,3-二亚胺铜配合物(II)的制品,所述基材例如是铜、硅片、在生产超大规模集成电路中使用的芯片、用具有比二氧化硅更低的介电常数的介电材料制备的芯片、以及涂有阻隔层的二氧化硅和低k基材。用于防止铜迁移的阻隔层包括钽、氮化钽、钛、氮化钛、氮化硅钽、氮化硅钛、氮化碳钽和氮化铌。
本发明人还发现了制备氨基亚胺化合物(1,3-二亚胺配体的前体)的新合成方法。McGeachin描述的文献方法需要使用昂贵且不稳定的烷基化试剂(四氟硼酸三乙基氧鎓)。更实用的工业规模方法必须以高产率进行,并使用稳定的更低成本的试剂。本申请人已经发现硫酸二甲酯和其它便宜的烷基化试剂可以用于代替四氟硼酸三乙基氧鎓盐。这些烷基化剂以高产率产生所需的氨基亚胺化合物,如下面的实施例所示。本发明还通过不需要使用助溶剂并简化了目标产物的分离过程来改进现有技术所述的方法。
本申请人的合成氨基亚胺化合物的方法包括:
a.使烷基亚氨基-单酮(III)与烷基化试剂接触,形成相应的O-烷基化衍生物(IV);
b.使步骤(a)的O-烷基化衍生物(IV)与伯烷基胺NH2R13接触,形成亚胺鎓盐(V);和
c.使步骤(b)的亚胺鎓盐(V)与强碱接触,形成相应的中性氨基亚胺(VI):
其中
R14和R11独立地选自H、C1-C5烷基、苯基、苄基和4-吡啶基;
R12是Me或Et;
R9和R13独立地选自H和C1-C5烷基,前提是在R9、R10、R11和R13中的碳总数是4-12;
烷基化试剂选自硫酸二甲酯、苯磺酸甲酯、甲苯磺酸甲酯、硫酸二乙酯、苯磺酸乙酯、三氟甲烷磺酸甲酯和甲苯磺酸乙酯;和
X-是衍生自烷基化试剂的阴离子。
在制备氨基亚胺化合物的上述方法中,烷基亚氨基-单酮(III)可以容易地从β-二酮与胺的反应获得。优选的伯烷基胺NH2R13选自甲胺、乙胺和丙胺。强碱选自甲醇钠、甲醇铜和叔丁醇钾。
在另一个实施方案中,本发明提供新的氨基亚胺化合物(VII)
其中
R14和R17独立地选自H、C1-C5烷基和二甲基氨基;和
R15和R16独立地选自H、C1-C5烷基、苯基、苄基和4-吡啶基,前提是R15或R16是4-吡啶基,和前提是在R14至R17中的碳总数是4-14。
优选的是,R14和R17是二甲基氨基,R15和R16是C1-C5烷基;或R15是4-吡啶基,R14、R16和R17是C1-C4烷基。
其中R14和R17独立地选自H、C1-C5烷基的氨基亚胺(VII)可以通过上述制备这些配体前体的方法来制备。其中R14和R17是二甲基氨基且R15和R16是甲基的氨基亚胺的制备在实施例7中给出;具有其它R15和R16取代基的类似的二甲基氨基配体可以类似地制备。
实施例
所有有机试剂从Sigma-Aldrich(940W.St.PaulAvenue,Milwaukee,WI,USA)获得。乙醇酮购自Alfa Aesar(30BondStreet,Ward Hill,MA,USA)。
实施例1
二(N-乙基-4-乙基亚氨基-2-戊烯-2-胺化)酮(II)的制备和还原
按照文献所述的方法(McGeachin)制备1,3-二亚胺配体,即CH3CH2N=C(CH3)-CH2-C(CH3)=N-CH2CH3·HBF4。铜(II)配合物通过游离碱与甲醇铜(II)在甲醇中反应来制备。将甲醇铜(0.268g)称量加入50ml的Erlenmeyer烧瓶中。加入磁力搅拌棒和5ml的甲醇。通过四氟硼酸盐(1.00g)与甲醇钠的反应制备游离的配体;甲醇盐溶液通过将NaH(0.105g)缓慢加入5ml甲醇中来制备。将该甲醇溶液一次全部与另外5ml甲醇一起加入快速搅拌的甲醇铜溶液中。立即形成了紫色溶液。将该混合物于室温搅拌1小时。真空除去溶剂。所得的固体与己烷混合;所得的混合物经由烧结的玻璃料用Celite545床过滤。滤饼用己烷洗涤,直到不再看到紫色。真空汽提出溶剂。在约100mTorr压力和40-115℃下的升华获得了熔点为98-110℃的固体。该材料的样品(约0.0250g)在约100mTorr压力和70-80℃下升华到用干冰冷却的玻璃冷指(cold finger)上。在玻璃表面上获得紫色膜。在冷却之后,含有铜配合物的釜用含有二乙基硅烷的釜代替。将该装置于50℃真空下加热。铜配合物的紫色褪成白色,然后变成淡淡的铜色,表明开始的铜配合物被还原成金属。
实施侧2
MeC(NHMe)=CHC(=O)Me的制备
将含水的甲胺(100g,在水中40%)滴加入100g的2,4-戊二酮中。这种添加温和地放热;添加速率调整到保持温度为约35-40℃。在完成添加之后,所得的黄色液体于室温搅拌1小时,然后进行真空蒸馏。将蒸馏釜在部分真空下加热,使得在30-35℃下获得第一蒸馏馏分(假设是水)。在除去该馏分之后,中止蒸馏。釜内的物料在冷却下固化。通过NMR分析,以良好的产率(大于90%)获得了标题化合物(纯度大于95%)。
实施例3
[MeC(NHMe)=CHC(=OMe)Me][MeOSO3]的制备
在干燥箱中,将实施例2的4-(甲基氨基)-3-戊烯-2-酮(1.00g)溶解在二氯甲烷(2ml)中,并与硫酸二甲酯(1.00g)混合。该混合物起初形成黄色溶液,在1小时的过程中冷却至可接触温度,在些许加热下形成浓浆液。过滤该浆液,用二氯甲烷洗涤固体,分离产率是0.90g(47%,基于硫酸二甲酯计)。固体产物的NMR谱与标题化合物相同。
在干燥箱中,将4-(甲基氨基)-3-戊烯-2-酮(1.08g)与二氯甲烷(0.5ml)混合,并将该浆液与硫酸二甲酯(1.00g)混合。先将所得溶液冷却至可接触温度,但在1小时的过程中固化,温度热得可接触。使该混合物在室温下在搅拌板上静置过夜,然后用于随后的下述反应。现场产率接近NMR谱量化值。
实施例4
[MeC(NHMe)=CHC(NHEt)Me][MeOSO3]的制备
将通过实施例9中方法制备的[MeC(NHMe)=CHC(=OMe)Me][MeOSO3]、二氯甲烷和未反应的过量MeC(NHMe)=CHC(=O)Me的固化混合物用2ml四氢呋喃第一次处理,然后用6ml(2M乙胺在四氢呋喃中)处理。所得的浆液在搅拌板温度(约30℃)下搅拌15分钟,然后过滤,干燥,得到1.63g的灰白色固体。NMR谱与以几种互变异构体的形式存在的标题组成相同,但没有获得绝对纯度。标题组合物的总的粗分离产率是81%,基于硫酸二甲酯计。
实施例5
二(N-甲基-4-乙基亚氨基-2-戊烯-2-胺化)铜(II)的制备
将1,3-二亚胺[MeC(NHMe)=CHC(NHEt)Me][MeOSO3](1.6g,如实施例4所述制备)溶解在15ml甲醇中。在搅拌下,加入叔丁醇钾(0.71g)。立即形成白色沉淀,在室温下搅拌15分钟后过滤除去该沉淀物。白色沉淀的1H NMR谱[D2O]与K[MeOSO3]相同。过滤的溶液用Cu(OCH3)2(0.40g)处理。所得的紫色浆液于室温搅拌过夜。除去溶剂,残余物被萃取入己烷中,通过过滤除去不溶性物质。己烷通过蒸发去除,留下标题化合物,是不纯的紫色糊状物。该物质通过于室温真空(约0.02托)下升华到干冰冷却的玻璃表面上或在高温(约100℃)下升华到室温下的玻璃表面上来提纯。
实施例6
用铜(II)1,3-二亚胺配合物评价还原剂
在干燥箱中,将选择的还原剂(10当量)滴加入(通过吸管)实施例1所述的铜配合物的深紫色溶液中(约7-16mg在5ml甲苯中)。将反应混合物逐步从室温加热到100℃。如果没有可观察到的变化,于100℃加入另外10当量的还原剂。
a)9-BBN(0.5M的四氢呋喃溶液)。深紫色溶液在于80℃加热时变成灰色/黑色。最后获得黑色沉淀物。黑色沉淀物表明形成了小的铜颗粒。
b)硼烷(1M的四氢呋喃溶液)。深紫色溶液立刻变透明,然后变成褐色/棕色,随后变成灰色/绿色。于45℃轻微加热,该溶液变黑。最后,形成了黑色沉淀物。
c)二氢苯并呋喃。深紫色溶液在于100℃加热时变暗。再加入10当量,该溶液逐渐变成暗的铜色溶液,其中含有褐色沉淀物。
d)吡唑啉。在加热时,深紫色溶液逐渐变蓝,然后变成绿色/灰色(77℃),然后变成绿色/铜色(85℃),最后变成黄色(100℃)。形成了褐色沉淀物。
e)二乙基硅烷。在加热(70-80℃)时,在管形瓶上形成黑色环,然后形成铜色的细致镜面。观察到黑色沉淀物。
实施例7
二(N-二甲基氨基-4-二甲基氨基亚氨基-2-戊烯-2-胺化)铜(II)的制备
将4.0g的戊烷-2,4-二酮和6.0g的N,N-二甲基肼的混合物于环境温度下搅拌过夜。该液体然后在压力下真空蒸馏,使得于89-90℃收集主要的馏出物。然后将0.92g的该馏出物与0.31g的甲醇铜(II)在5ml甲醇中混合,于环境温度下搅拌3天。过滤该溶液,然后蒸发成紫色油,它可溶于己烷且是可升华的(约100℃,0.015托)。
实施例8
二(N-甲基-4-甲基亚氨基-4-苯基-2-丁烯-2-胺化)铜(II)的制备和还原
按照文献所述的方法(McGeachin)制备1,3-二亚胺配体,即CH3N=C(CH3)-CH2-C(C6H5)=N-CH3·HBF4。铜(II)配合物通过游离碱与乙醇铜(II)在四氢呋喃中反应来制备;游离碱通过四氟硼酸盐与甲醇钠的反应来制备(实施例1)。将乙醇铜(0.408g)称量加入50ml烧瓶中。加入磁力搅拌棒和约30ml。将在几毫升四氢呋喃中的游离碱配体(1.00g)一次加入快速搅拌的乙醇铜溶液中。立即形成了紫色溶液。将该混合物于室温搅拌过夜,然后经由烧结的玻璃料用Celite545床过滤。真空汽提出溶剂,获得干燥的固体。在约100mTorr压力和110-120℃下的升华获得了熔点为98-100℃的固体。
将铜(II)配合物(约0.018g)放入管形瓶中,然后将其放入管中。将该管用氮气流加热到165℃(入口压力是5托);该管的出口压力是30mTorr或更低。该管中的第二区域(朝向管的出口)保持在100℃。铜样品从初始区域升华并在冷却区沉积,这由管壁上的紫色沉积物证实。将该装置排空,然后用二乙基硅烷反填充。铜沉积物在玻璃壁上在100℃区域中形成,这由紫色的消失和出现铜色沉淀物来证实。
实施例9
N,N’-二乙基-2,4-戊二酮亚胺的制备
在干燥箱中,向250ml圆底烧瓶中加入4-(乙基氨基)-3-戊烯-2-酮(30.0g,237mmol)和硫酸二甲酯(30.0g,238mmol)。将反应溶液搅拌,然后静置(12小时),得到粘性油。在剧烈搅拌下加入乙胺在THF(150ml)中的2M溶液。搅拌该溶液(1小时)直至它固化。中间体盐可以分离(如实施例4的方法所述)或直接使用。
将甲醇钠(12.8g,237mmol)在甲醇(40ml)中的溶液加入中间体盐(vida supra),并于环境温度搅拌(1小时)。除去溶剂(真空),得到油状物,用戊烷萃取,过滤,浓缩,得到粗的黄色油。产物N,N’-二乙基-2,4-戊二酮亚胺通过分馏分离,得到黄色油(28.6g),产率是72%,基于初始的4-(乙基氨基)-3-戊烯-2-酮计。
Claims (17)
1、一种在基材上形成铜沉积物的方法,包括:
a.使基材与铜配合物(I)接触,形成铜配合物在该基材上的沉积物;和
b.使沉积的铜配合物与还原剂接触,其中
R1和R4独立地选自H、C1-C5烷基和二甲基氨基;
R2和R3独立地选自H、C1-C5烷基、苯基、苄基和4-吡啶基,前提是在R1至R4中的碳总数是4-12;和
还原剂选自9-BBN、硼烷、二氢苯并呋喃、吡唑啉、二乙基硅烷、二甲基硅烷、乙基硅烷、甲基硅烷、苯基硅烷和硅烷。
2、根据权利要求1的方法,其中R1、R3和R4是甲基,R2是苯基。
3、根据权利要求1的方法,其中基材选自铜、硅片和涂有阻隔层的二氧化硅。
4、根据权利要求1的方法,其中基材暴露于铜配合物的蒸气中。
5、根据权利要求1的方法,其中沉积在0-120℃下进行。
6、根据权利要求1的方法,其中还原剂是硅烷或二乙基硅烷。
7、1,3-二亚胺铜配合物(II)
其中
R5和R8是二甲基氨基;和
R6和R7独立地选自H、C1-C5烷基、苯基、苄基和4-吡啶基,前提是在R5至R8中的碳总数是4-14;或
R5和R8独立地选自H、C1-C5烷基和二甲基氨基;和
R6和R7选自H、C1-C5烷基、苯基、苄基和4-吡啶基,前提是R6或R7是4-吡啶基,和前提是在R5至R8中的碳总数是4-14。
8、根据权利要求7的1,3-二亚胺铜配合物,其中R5和R8是二甲基氨基。
9、一种含有沉积在基材上的权利要求7的1,3-二亚胺铜配合物(II)的制品。
10、根据权利要求9的制品,其中基材选自铜、硅片和涂有阻隔层的二氧化硅。
11、根据权利要求10的制品,其中阻隔层选自钽、氮化钽、钛、氮化钛、氮化硅钽、氮化硅钛、氮化碳钽和氮化铌。
12、一种合成二亚胺化合物的方法,包括:
a.使烷基亚氨基-单酮(III)与烷基化试剂接触,形成相应的O-烷基化衍生物(IV);
b.使步骤(a)的O-烷基化衍生物(IV)与伯烷基胺NH2R13接触,形成亚胺鎓盐(V);和
c.使步骤(b)的亚胺鎓盐(V)与强碱接触,形成相应的中性氨基亚胺(VI):
其中
R10和R11独立地选自H、C1-C5烷基、苯基、苄基和4-吡啶基;
R12是Me或Et;
R9和R13独立地选自H和C1-C5烷基,前提是在R9、R10、R11和R13中的碳总数是4-12;
烷基化试剂选自硫酸二甲酯、苯磺酸甲酯、甲苯磺酸甲酯、硫酸二乙酯、苯磺酸乙酯、三氟甲烷磺酸甲酯和甲苯磺酸乙酯;和
X-是衍生自烷基化试剂的阴离子。
13、根据权利要求12的方法,其中烷基化试剂是硫酸二甲酯。
14、根据权利要求12的方法,其中R13选自甲基、乙基和正丙基。
15、根据权利要求12的方法,其中强碱选自甲醇钠、甲醇铜和叔丁醇钾。
16、一种组合物,含有氨基亚胺化合物(VII)
其中
R14和R17独立地选自H、C1-C5烷基和二甲基氨基;和
R15和R16选自H、C1-C5烷基、苯基、苄基和4-吡啶基,前提是R15或R16是4-吡啶基,和前提是在R14至R17中的碳总数是4-14。
17、根据权利要求16的氨基亚胺化合物,其中R15是4-吡啶基,R14、R16和R17是C1-C4烷基。
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TWI842668B (zh) | 2017-02-08 | 2024-05-21 | 加拿大國家研究委員會 | 具低黏度與低加工溫度之銀分子油墨 |
TW201842087A (zh) | 2017-02-08 | 2018-12-01 | 加拿大國家研究委員會 | 具改良之熱穩定性的分子油墨 |
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US3594216A (en) * | 1969-06-19 | 1971-07-20 | Westinghouse Electric Corp | Vapor phase deposition of metal from a metal-organic beta-ketoamine chelate |
DE4202889C2 (de) | 1992-02-01 | 1994-12-15 | Solvay Deutschland | Verfahren zur Abscheidung von ein Metall der ersten Übergangsmetallreihe oder Aluminium enthaltenden Schichten und 1,3-Diketiminato-Metall-Verbindungen |
US5464666A (en) * | 1995-02-06 | 1995-11-07 | Air Products And Chemicals, Inc. | Process for chemical vapor codeposition of copper and aluminum alloys |
US6620956B2 (en) * | 2001-11-16 | 2003-09-16 | Applied Materials, Inc. | Nitrogen analogs of copper II β-diketonates as source reagents for semiconductor processing |
WO2003044242A2 (en) | 2001-11-16 | 2003-05-30 | Applied Materials, Inc. | Atomic layer deposition of copper using a reducing gas and non-fluorinated copper precursors |
US6484666B1 (en) | 2001-11-21 | 2002-11-26 | Allied Precision Industries Inc. | Bird bath |
JP2005520053A (ja) * | 2002-01-18 | 2005-07-07 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | 原子層堆積によって銅薄膜を堆積させるための揮発性銅(ii)錯体 |
US20050227007A1 (en) * | 2004-04-08 | 2005-10-13 | Bradley Alexander Z | Volatile copper(I) complexes for deposition of copper films by atomic layer deposition |
US20040247905A1 (en) * | 2003-04-16 | 2004-12-09 | Bradley Alexander Zak | Volatile copper(I) complexes for deposition of copper films by atomic layer deposition |
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2003
- 2003-01-17 JP JP2004503688A patent/JP2005520053A/ja active Pending
- 2003-01-17 US US10/346,874 patent/US6939578B2/en not_active Expired - Fee Related
- 2003-01-17 KR KR10-2004-7011062A patent/KR20040077733A/ko not_active Application Discontinuation
- 2003-01-21 AU AU2003210599A patent/AU2003210599A1/en not_active Abandoned
- 2003-01-21 CN CNB038023024A patent/CN100360709C/zh not_active Expired - Fee Related
- 2003-01-21 WO PCT/US2003/001846 patent/WO2003095701A1/en active Application Filing
- 2003-01-21 US US10/499,934 patent/US20050003075A1/en not_active Abandoned
- 2003-01-21 EP EP20030750016 patent/EP1466032A1/en not_active Withdrawn
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2004
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- 2004-12-20 US US11/017,166 patent/US7087774B2/en not_active Expired - Fee Related
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102341525A (zh) * | 2009-02-19 | 2012-02-01 | 东京毅力科创株式会社 | Cu膜的成膜方法和存储介质 |
CN116791362A (zh) * | 2023-05-17 | 2023-09-22 | 邵阳阳光发品有限公司 | 一种抗断裂性能优异的抗菌假发及其制备方法 |
CN116791362B (zh) * | 2023-05-17 | 2024-05-10 | 邵阳阳光发品有限公司 | 一种抗断裂性能优异的抗菌假发及其制备方法 |
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US7186835B2 (en) | 2007-03-06 |
US7388113B2 (en) | 2008-06-17 |
US6939578B2 (en) | 2005-09-06 |
US20060237718A1 (en) | 2006-10-26 |
JP2005520053A (ja) | 2005-07-07 |
US20050003075A1 (en) | 2005-01-06 |
US7268365B2 (en) | 2007-09-11 |
US20050158479A1 (en) | 2005-07-21 |
US20050107283A1 (en) | 2005-05-19 |
EP1466032A1 (en) | 2004-10-13 |
KR20040077733A (ko) | 2004-09-06 |
US20050267305A1 (en) | 2005-12-01 |
US7087774B2 (en) | 2006-08-08 |
AU2003210599A1 (en) | 2003-11-11 |
CN100360709C (zh) | 2008-01-09 |
US20030232142A1 (en) | 2003-12-18 |
WO2003095701A1 (en) | 2003-11-20 |
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