CN109071571B - 过渡金属化合物、其制造方法及包含其的含过渡金属薄膜蒸镀用组合物 - Google Patents
过渡金属化合物、其制造方法及包含其的含过渡金属薄膜蒸镀用组合物 Download PDFInfo
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- CN109071571B CN109071571B CN201780023511.7A CN201780023511A CN109071571B CN 109071571 B CN109071571 B CN 109071571B CN 201780023511 A CN201780023511 A CN 201780023511A CN 109071571 B CN109071571 B CN 109071571B
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- 239000010409 thin film Substances 0.000 title claims abstract description 81
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 59
- 150000003624 transition metals Chemical group 0.000 title claims abstract description 57
- 150000003623 transition metal compounds Chemical class 0.000 title claims abstract description 49
- 239000000203 mixture Substances 0.000 title claims abstract description 35
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 33
- 238000007740 vapor deposition Methods 0.000 title claims abstract description 29
- 239000000126 substance Substances 0.000 claims description 86
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 39
- 150000001875 compounds Chemical class 0.000 claims description 29
- 229910052726 zirconium Inorganic materials 0.000 claims description 22
- 125000003282 alkyl amino group Chemical group 0.000 claims description 20
- 239000010408 film Substances 0.000 claims description 19
- 229910052735 hafnium Chemical group 0.000 claims description 19
- 239000000758 substrate Substances 0.000 claims description 18
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical group [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 17
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 14
- 239000010936 titanium Substances 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 229910052719 titanium Inorganic materials 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
- 229910000326 transition metal silicate Inorganic materials 0.000 claims description 7
- 125000004069 aziridinyl group Chemical group 0.000 claims description 5
- 125000000719 pyrrolidinyl group Chemical group 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims 12
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims 4
- 125000003725 azepanyl group Chemical group 0.000 claims 4
- 125000003386 piperidinyl group Chemical group 0.000 claims 4
- 229910044991 metal oxide Inorganic materials 0.000 claims 2
- 150000004706 metal oxides Chemical class 0.000 claims 2
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 description 75
- 125000006736 (C6-C20) aryl group Chemical group 0.000 description 60
- -1 zirconium alkoxide Chemical class 0.000 description 40
- 239000002243 precursor Substances 0.000 description 37
- 125000003545 alkoxy group Chemical group 0.000 description 35
- 238000006243 chemical reaction Methods 0.000 description 35
- 239000002904 solvent Substances 0.000 description 31
- 229910052710 silicon Inorganic materials 0.000 description 27
- MAUMSNABMVEOGP-UHFFFAOYSA-N (methyl-$l^{2}-azanyl)methane Chemical compound C[N]C MAUMSNABMVEOGP-UHFFFAOYSA-N 0.000 description 24
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 22
- 238000003786 synthesis reaction Methods 0.000 description 22
- 125000000217 alkyl group Chemical group 0.000 description 20
- 239000006227 byproduct Substances 0.000 description 18
- 125000000592 heterocycloalkyl group Chemical group 0.000 description 18
- 238000000034 method Methods 0.000 description 17
- 238000005160 1H NMR spectroscopy Methods 0.000 description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- 238000004821 distillation Methods 0.000 description 14
- 125000006651 (C3-C20) cycloalkyl group Chemical group 0.000 description 13
- 125000004448 alkyl carbonyl group Chemical group 0.000 description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- 238000000231 atomic layer deposition Methods 0.000 description 12
- 125000006254 cycloalkyl carbonyl group Chemical group 0.000 description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 11
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 11
- 239000010703 silicon Substances 0.000 description 11
- 239000007789 gas Substances 0.000 description 10
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 9
- 125000003118 aryl group Chemical group 0.000 description 9
- 125000000753 cycloalkyl group Chemical group 0.000 description 9
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 8
- 125000006701 (C1-C7) alkyl group Chemical group 0.000 description 7
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 7
- 125000003277 amino group Chemical group 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 7
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 7
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 125000003710 aryl alkyl group Chemical group 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- 125000003368 amide group Chemical group 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000012159 carrier gas Substances 0.000 description 5
- UHOVQNZJYSORNB-MICDWDOJSA-N deuteriobenzene Chemical compound [2H]C1=CC=CC=C1 UHOVQNZJYSORNB-MICDWDOJSA-N 0.000 description 5
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 5
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 5
- 239000003446 ligand Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 5
- 239000012495 reaction gas Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 5
- 229910001928 zirconium oxide Inorganic materials 0.000 description 5
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 4
- ZMJTWCSLURLKQU-UHFFFAOYSA-N N-[cyclopenta-2,4-dien-1-ylmethyl(dimethyl)silyl]methanamine Chemical compound CN[Si](C)(C)CC1C=CC=C1 ZMJTWCSLURLKQU-UHFFFAOYSA-N 0.000 description 4
- FBRJAGMAWJXZMS-UHFFFAOYSA-N N-[cyclopenta-2,4-dien-1-ylmethyl(dimethyl)silyl]propan-1-amine Chemical compound C(CC)N[Si](C)(C)CC1C=CC=C1 FBRJAGMAWJXZMS-UHFFFAOYSA-N 0.000 description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 125000002950 monocyclic group Chemical group 0.000 description 4
- 230000000737 periodic effect Effects 0.000 description 4
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 4
- 238000000427 thin-film deposition Methods 0.000 description 4
- YKPQUSLRUFLVDA-UHFFFAOYSA-N $l^{2}-azanylmethane Chemical compound [NH]C YKPQUSLRUFLVDA-UHFFFAOYSA-N 0.000 description 3
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- DWCMDRNGBIZOQL-UHFFFAOYSA-N dimethylazanide;zirconium(4+) Chemical compound [Zr+4].C[N-]C.C[N-]C.C[N-]C.C[N-]C DWCMDRNGBIZOQL-UHFFFAOYSA-N 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 229910017053 inorganic salt Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- FVZVCSNXTFCBQU-UHFFFAOYSA-N phosphanyl Chemical group [PH2] FVZVCSNXTFCBQU-UHFFFAOYSA-N 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 125000003367 polycyclic group Chemical group 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- JQUZTGJSSQCTPV-UHFFFAOYSA-N sodium;cyclopenta-1,3-diene Chemical compound [Na+].C1C=CC=[C-]1 JQUZTGJSSQCTPV-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- BDQFVVWKFPJXLI-UHFFFAOYSA-N ClC[SiH](C)C.[Cl] Chemical compound ClC[SiH](C)C.[Cl] BDQFVVWKFPJXLI-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- CLOQWDQMYGISND-UHFFFAOYSA-N N-[cyclopenta-2,4-dien-1-ylmethyl(dimethyl)silyl]propan-2-amine Chemical compound C(C)(C)N[Si](C)(C)CC1C=CC=C1 CLOQWDQMYGISND-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 2
- ZYLGGWPMIDHSEZ-UHFFFAOYSA-N dimethylazanide;hafnium(4+) Chemical compound [Hf+4].C[N-]C.C[N-]C.C[N-]C.C[N-]C ZYLGGWPMIDHSEZ-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
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- 238000004518 low pressure chemical vapour deposition Methods 0.000 description 2
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
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- 229920000728 polyester Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
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- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
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- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 125000006413 ring segment Chemical group 0.000 description 2
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- MNWRORMXBIWXCI-UHFFFAOYSA-N tetrakis(dimethylamido)titanium Chemical compound CN(C)[Ti](N(C)C)(N(C)C)N(C)C MNWRORMXBIWXCI-UHFFFAOYSA-N 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 2
- AIRXBOWCKMAJHG-UHFFFAOYSA-N C(CC)N[Zr](N(C)C)([SiH](C)C)CC1C=CC=C1 Chemical compound C(CC)N[Zr](N(C)C)([SiH](C)C)CC1C=CC=C1 AIRXBOWCKMAJHG-UHFFFAOYSA-N 0.000 description 1
- DCUOTHLKSCHEME-UHFFFAOYSA-N CN[Zr](N(C)C)([SiH](C)C)CC1C=CC=C1 Chemical compound CN[Zr](N(C)C)([SiH](C)C)CC1C=CC=C1 DCUOTHLKSCHEME-UHFFFAOYSA-N 0.000 description 1
- 102100037709 Desmocollin-3 Human genes 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910005540 GaP Inorganic materials 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- 229910004129 HfSiO Inorganic materials 0.000 description 1
- 101000968042 Homo sapiens Desmocollin-2 Proteins 0.000 description 1
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- 238000005481 NMR spectroscopy Methods 0.000 description 1
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- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910003811 SiGeC Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910000577 Silicon-germanium Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 229910007932 ZrCl4 Inorganic materials 0.000 description 1
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- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000000277 atomic layer chemical vapour deposition Methods 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
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- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- ITKVLPYNJQOCPW-UHFFFAOYSA-N chloro-(chloromethyl)-dimethylsilane Chemical compound C[Si](C)(Cl)CCl ITKVLPYNJQOCPW-UHFFFAOYSA-N 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
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- 239000013256 coordination polymer Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 125000004663 dialkyl amino group Chemical group 0.000 description 1
- 125000000031 ethylamino group Chemical group [H]C([H])([H])C([H])([H])N([H])[*] 0.000 description 1
- 125000004672 ethylcarbonyl group Chemical group [H]C([H])([H])C([H])([H])C(*)=O 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
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- RMBPEFMHABBEKP-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2C3=C[CH]C=CC3=CC2=C1 RMBPEFMHABBEKP-UHFFFAOYSA-N 0.000 description 1
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- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- BNRNAKTVFSZAFA-UHFFFAOYSA-N hydrindane Chemical compound C1CCCC2CCCC21 BNRNAKTVFSZAFA-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- RPQDHPTXJYYUPQ-UHFFFAOYSA-N indium arsenide Chemical compound [In]#[As] RPQDHPTXJYYUPQ-UHFFFAOYSA-N 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
- 125000004674 methylcarbonyl group Chemical group CC(=O)* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910003465 moissanite Inorganic materials 0.000 description 1
- 125000002004 n-butylamino group Chemical group [H]N(*)C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000004888 n-propyl amino group Chemical group [H]N(*)C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000006252 n-propylcarbonyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C(*)=O 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000002868 norbornyl group Chemical group C12(CCC(CC1)C2)* 0.000 description 1
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000005328 phosphinyl group Chemical group [PH2](=O)* 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000012994 photoredox catalyst Substances 0.000 description 1
- 125000005936 piperidyl group Chemical group 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000012686 silicon precursor Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 125000006253 t-butylcarbonyl group Chemical group [H]C([H])([H])C(C(*)=O)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000006318 tert-butyl amino group Chemical group [H]N(*)C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
- XLMQAUWIRARSJG-UHFFFAOYSA-J zirconium(iv) iodide Chemical compound [Zr+4].[I-].[I-].[I-].[I-] XLMQAUWIRARSJG-UHFFFAOYSA-J 0.000 description 1
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Abstract
本发明涉及新型过渡金属化合物、其制造方法、包含其的含过渡金属薄膜蒸镀用组合物、利用含过渡金属薄膜蒸镀用组合物的含过渡金属薄膜和含过渡金属薄膜的制造方法,本发明的过渡金属化合物的热稳定性高,挥发性高,储存稳定性高,从而将其用作前体能够容易地制造出高密度和高纯度的含过渡金属薄膜。
Description
技术领域
本发明涉及一种新型过渡金属化合物、其制造方法及包含其的含过渡金属薄膜蒸镀用组合物,更详细而言,能够有用地用作含过渡金属薄膜的前体的新型过渡金属化合物、其制造方法、包含其的含过渡金属薄膜蒸镀用组合物、利用含过渡金属薄膜蒸镀用组合物的含过渡金属薄膜及含过渡金属薄膜的制造方法。
背景技术
在半导体工艺中,作为栅极电介质,一直以来主要使用硅氧化物(SiO2)。这种硅氧化物虽然制造工艺简单,但具有比较低的介电常数,因此在厚度薄的情况下,存在发生从栅极到沟道的漏电流(gate-to-channel leakage current)的问题。
为了解决这种问题,正在积极进行对于作为绝缘性优异、介电常数高而介电损耗低的高介电物质的high-k物质的研究。
进而,随着半导体结构集成化、微细化,为了能够适用于在精细图案中也能够具有优异的阶梯覆盖性的各种工序(作为一个例子,原子层沉积法(ALD:atomic layerdeposition)、化学气相沉积法(CVD:chemical vapor deposition)),作为高介电物质,对于具有较高的热稳定性、挥发性高、尽可能在常温下为液体的前体化合物的要求越来越高。
作为一个例子,利用锆前体且用原子层沉积法或化学气相沉积法的锆氧化物薄膜的制造根据锆前体的配体结构而发展成各种形式。
利用ZrCl4、ZrI4、ZrF4等无机盐并通过原子层沉积法或化学气相沉积法而制造的锆氧化物薄膜存在由于薄膜内部残留无机盐(Cl-、F-、I-)而薄膜的电性特性劣化,容易发生薄膜的凝聚(aggromeration)现象的问题。此外,还具有无法任意调整锆氧化膜的粗糙度,也难以调整薄膜厚度的缺点。
Master.Chem.,1994,4,1815中公开了利用锆醇盐前体的锆氧化物薄膜,作为前体使用Zr(OtBu)4。但是,Zr(OtBu)4的反应性非常高而在薄膜制造工序中处理起来非常棘手,有微量的水分也会发生催化水解(catalytic hydrolytic decomposition)反应,因此具有储存寿命非常短的缺点。
另外,Chem.Mater.,2002,14,4350中公开了将配位有酰胺配体的锆化合物作为前体而形成的锆氧化物薄膜。以Zr(NMeEt)4或Zr(NEt2)4为代表的锆酰胺化合物在常温下均以粘性低的液体状态存在,蒸汽压非常高,利用臭氧和水蒸气而容易去除酰胺配体,因此作为利用原子层沉积法工艺的ZrO2薄膜制造的前体而最广泛地被利用。但是,最近已知这种锆酰胺化合物的反应性非常高,不容易长期保管,特别是热稳定性低,在气化过程中分解而大大影响薄膜的品质。
虽然正在努力完善以上提及的现有的无机盐、醇盐、酰胺配体具有的缺点,增加锆前体的热稳定性,并公开了如具有环戊二烯(Cp:cyclopentadiene)基作为配体的CpZr(N(CH3)2)3等锆前体,但目前为止没有得到令人满意的结果。
因此,目前依然需要进行对于与作为现有的薄膜蒸镀用前体而使用的化合物相比具有更优异的特性的薄膜蒸镀用前体的研究。
发明内容
因此,本发明为了解决如上所述的问题,提供一种热稳定性优异而可用作薄膜蒸镀用前体的过渡金属化合物及其制造方法。
另外,本发明提供包含本发明的过渡金属化合物的含过渡金属薄膜蒸镀用组合物、利用其制造的含过渡金属薄膜及利用其的含过渡金属薄膜的制造方法。
本发明提供挥发性高、热稳定性优异、具有优异的凝聚力而可用作薄膜蒸镀的前体的过渡金属化合物,本发明的过渡金属化合物由下述化学式1表示。
[化学式1]
[上述化学式1中,
M为元素周期表中的第4族的过渡金属;
R1至R4彼此独立地为氢原子或(C1-C20)烷基;
R5和R6彼此独立地为氢原子、(C1-C20)烷基、(C6-C20)芳基、(C6-C20)芳基(C1-C20)烷基或(C1-C20)烷氧基;
A为-(CR11R12)a-,R11和R12彼此独立地为氢、(C1-C20)烷基、(C6-C20)芳基、(C6-C20)芳基(C1-C20)烷基或(C1-C20)烷氧基,a为1至3的整数;
D为-N(R13)-,R13为氢原子、(C1-C20)烷基、(C3-C20)环烷基、(C6-C20)芳基、(C6-C20)芳基(C1-C20)烷基、(C1-C20)烷基羰基或(C3-C20)环烷基羰基;
X彼此独立地为(C1-C20)烷基、(C6-C20)芳基、(C6-C20)芳基(C1-C20)烷基、(C1-C20)烷氧基、被(C3-C20)烷基取代或未取代的甲硅烷基、(C3-C20)杂环烷基、被(C1-C20)烷基或(C6-C20)芳基取代或未取代的氨基、被(C1-C20)烷基或(C6-C20)芳基取代或未取代的酰胺基、被(C1-C20)烷基或(C6-C20)芳基取代或未取代的膦基、被(C1-C20)烷基或(C6-C20)芳基取代或未取代的次膦基(포스피도기,phosphido group),其中,X为环戊二烯基衍生物的情况除外;
上述R1至R6、A、D和X的烷基、环烷基、芳基、芳基烷基、烷基羰基、环烷基羰基或烷氧基还可以被(C1-C20)烷基、(C3-C20)环烷基、(C6-C20)芳基或(C6-C20)芳基(C10-C20)烷基取代;
n为1或2的整数。]
优选地,根据本发明的一实施例的上述化学式1中,M可以为钛、锆或铪,R1至R6可以彼此独立地为氢原子或(C1-C7)烷基。
优选地,根据本发明的一实施例的上述化学式1中,R11至R13可以彼此独立地为氢原子或(C1-C20)烷基,X可以彼此独立地为被(C1-C20)烷基或(C6-C20)芳基取代或未取代的氨基、被(C1-C20)烷基或(C6-C20)芳基取代或未取代的酰胺基、(C1-C20)烷基、(C3-C20)杂环烷基或(C1-C20)烷氧基。
优选地,根据本发明的一实施例的上述化学式1中,M可以为锆、铪或钛;R1至R6可以彼此独立地为氢原子或(C1-C7)烷基;X可以彼此独立地为被(C1-C20)烷基取代的氨基、(C1-C20)烷基、(C3-C20)杂环烷基或(C1-C20)烷氧基。
根据本发明的一实施例的上述化学式1的过渡金属化合物可以选自下述化合物。
本发明提供制造由下述化学式1表示的过渡金属化合物的方法,本发明的下述化学式1包括使下述化学式2和化学式3反应而制造由下述化学式1表示的过渡金属化合物的步骤。
[化学式1]
[化学式2]
[化学式3]
M(X)4
[上述化学式1至3中,
M为元素周期表中的第4族的过渡金属;
R1至R4彼此独立地为氢原子或(C1-C20)烷基;
R5和R6彼此独立地为氢原子、(C1-C20)烷基、(C6-C20)芳基、(C6-C20)芳基(C1-C20)烷基或(C1-C20)烷氧基;
A为-(CR11R12)a-,R11和R12彼此独立地为氢、(C1-C20)烷基、(C6-C20)芳基、(C6-C20)芳基(C1-C20)烷基或(C1-C20)烷氧基,a为1至3的整数;
D为-N(R13)-,R13为氢原子、(C1-C20)烷基、(C3-C20)环烷基、(C6-C20)芳基、(C6-C20)芳基(C1-C20)烷基、(C1-C20)烷基羰基或(C3-C20)环烷基羰基;
X彼此独立地为(C1-C20)烷基、(C6-C20)芳基、(C6-C20)芳基(C1-C20)烷基、(C1-C20)烷氧基、被(C3-C20)烷基取代或未取代的甲硅烷基、(C3-C20)杂环烷基、被(C1-C20)烷基或(C6-C20)芳基取代或未取代的氨基、被(C1-C20)烷基或(C6-C20)芳基取代或未取代的酰胺基、被(C1-C20)烷基或(C6-C20)芳基取代或未取代的膦基、被(C1-C20)烷基或(C6-C20)芳基取代或未取代的次膦基,其中,X为环戊二烯基衍生物的情况除外;
上述R1至R6、A、D和X的烷基、环烷基、杂环烷基、芳基、芳基烷基、烷基羰基、环烷基羰基或烷氧基还可以被(C1-C20)烷基、(C3-C20)环烷基、(C6-C20)芳基或(C6-C20)芳基(C10-C20)烷基取代;
n为1或2的整数。]
根据本发明的一实施例的化学式2可以在使下述化学式4和化学式5反应而制造下述化学式6后,使下述化学式6与下述化学式7反应而制造。
[化学式4]
[化学式5]
DH2
[化学式6]
[化学式7]
M1-C5H(R1)(R2)(R3)(R4)
[上述化学式4至7中,
M1为碱金属;
R1至R4彼此独立地为氢原子或(C1-C20)烷基;
R5和R6彼此独立地为氢原子、(C1-C20)烷基、(C6-C20)芳基、(C6-C20)芳基(C1-C20)烷基或(C1-C20)烷氧基;
A为-(CR11R12)a-,R11和R12彼此独立地为氢、(C1-C20)烷基、(C6-C20)芳基、(C6-C20)芳基(C1-C20)烷基或(C1-C20)烷氧基,a为1至3的整数;
D为-N(R13)-,R13为氢原子、(C1-C20)烷基、(C3-C20)环烷基、(C6-C20)芳基、(C6-C20)芳基(C1-C20)烷基、(C1-C20)烷基羰基或(C3-C20)环烷基羰基;
上述R1至R6、A和D的烷基、环烷基、芳基、芳基烷基、烷基羰基、环烷基羰基或烷氧基还可以被(C1-C20)烷基、(C3-C20)环烷基、(C6-C20)芳基或(C6-C20)芳基(C10-C20)烷基取代;
X1和X2彼此独立地为卤素基团;
n为1或2的整数。]
另外,本发明提供包含本发明的过渡金属化合物的含过渡金属薄膜蒸镀用组合物。
优选地,包含在本发明的含过渡金属薄膜蒸镀用组合物的过渡金属化合物的过渡金属可以为锆、铪或钛。
另外,本发明提供利用本发明的含过渡金属薄膜蒸镀用组合物制造的含过渡金属薄膜和含过渡金属薄膜的制造方法。
本发明的新型过渡金属化合物的挥发性高、热稳定性和凝聚力优异而可用作含过渡金属薄膜的前体。
另外,本发明的新型过渡金属化合物的熔点低而在常温下大部分以液体状态存在,热稳定性高而储存稳定性非常优异。
本发明的含过渡金属薄膜蒸镀用组合物包含热稳定性高的本发明的过渡金属化合物作为前体,从而可适用于各种薄膜蒸镀方法,利用其制造的薄膜密度和纯度高。
本发明的含过渡金属薄膜蒸镀用组合物包含挥发性高、热稳定性和凝聚力优异、熔点低而在常温下大部分以液体状态存在的本发明的过渡金属化合物作为前体,从而在形成利用其的过渡金属薄膜时,具有优异的阶梯覆盖性,能够得到密度高的高纯度薄膜。
附图说明
图1是表示实验例2的阶梯覆盖特性的图,
图2是表示实验例3的阶梯覆盖特性的图,
图3是表示实验例4的阶梯覆盖特性的图。
具体实施方式
下面,对本发明的新型过渡金属化合物和其制造方法详细说明,这时使用的技术用语和科学用语只要没有其他定义,则具有该发明所属技术领域中具有常规知识的人员通常理解的意思,下述说明中省略对于可能不必要地混淆本发明的主旨的公知功能和构成的说明。
本发明提供挥发性高、热稳定性优异且具有优异的凝聚力的、由下述化学式1表示的过渡金属化合物。
[化学式1]
[上述化学式1中,
M为元素周期表中的第4族的过渡金属;
R1至R4彼此独立地为氢原子或(C1-C20)烷基;
R5和R6彼此独立地为氢原子、(C1-C20)烷基、(C6-C20)芳基、(C6-C20)芳基(C1-C20)烷基或(C1-C20)烷氧基;
A为-(CR11R12)a-,R11和R12彼此独立地为氢、(C1-C20)烷基、(C6-C20)芳基、(C6-C20)芳基(C1-C20)烷基或(C1-C20)烷氧基,a为1至3的整数;
D为-N(R13)-,R13为氢原子、(C1-C20)烷基、(C3-C20)环烷基、(C6-C20)芳基、(C6-C20)芳基(C1-C20)烷基、(C1-C20)烷基羰基或(C3-C20)环烷基羰基;
X彼此独立地为(C1-C20)烷基、(C6-C20)芳基、(C6-C20)芳基(C1-C20)烷基、(C1-C20)烷氧基、被(C3-C20)烷基取代或未取代的硅氧基、(C3-C20)杂环烷基、被(C1-C20)烷基或(C6-C20)芳基取代或未取代的氨基、被(C1-C20)烷基或(C6-C20)芳基取代或未取代的酰胺基、被(C1-C20)烷基或(C6-C20)芳基取代或未取代的膦基、被(C1-C20)烷基或(C6-C20)芳基取代或未取代的次膦基,其中,X为环戊二烯基衍生物的情况除外;
上述R1至R6、A、D和X的烷基、环烷基、芳基、芳基烷基、烷基羰基、环烷基羰基或烷氧基还可以被(C1-C20)烷基、(C3-C20)环烷基、(C6-C20)芳基或(C6-C20)芳基(C10-C20)烷基取代;
n为1或2的整数。]
本发明的由上述化学式1表示的过渡金属化合物挥发性高、热稳定性高而可以容易地用作制造含有过渡金属的薄膜的前体。
另外,本发明的由上述化学式1表示的过渡金属化合物的熔点低而在常温下大部分以液体状态存在,从而储存稳定性高,因此利用这一特点能够以高密度制造高纯度的薄膜。
另外,为了制造过渡金属硅酸盐薄膜,与将各个过渡金属前体和硅前体各自两个的混合物作为前体使用的现有技术不同,本发明的由上述化学式1表示的过渡金属化合物中硅与过渡金属包含在一个分子中,能够只用一个前体制造过渡金属硅酸盐薄膜,既经济又高效、薄膜的纯度非常优异。
具体而言,根据本发明的一实施例的X可以彼此独立地为(C1-C20)烷基、(C3-C20)杂环烷基、(C6-C20)芳基、(C6-C20)芳基(C1-C20)烷基、(C1-C20)烷氧基、被(C3-C20)烷基取代的硅氧基、单(C1-C20)烷基氨基、二(C1-C20)烷基氨基、单(C1-C20)烷基酰胺基、二(C1-C20)烷基酰胺基、被(C1-C20)烷基取代的膦基或被(C1-C20)烷基取代的次膦基,可以优选为被(C1-C20)烷基取代的氨基、(C1-C20)烷基、(C3-C20)杂环烷基或(C1-C20)烷氧基,可以更优选为单(C1-C20)烷基氨基、二(C1-C20)烷基氨基、或(C3-C20)杂环烷基,其中可以不包括X为环戊二烯基衍生物的情况。
优选地,在提高介电常数方面,根据本发明的一实施例的M可以为钛、锆或铪。
优选地,根据本发明的一实施例的R1至R6可以彼此独立地为氢原子或(C1-C7)烷基,具体而言,可以彼此独立地为氢原子、甲基、乙基、正丙基、异丙基、正丁基、仲丁基、叔丁基或正戊基。
优选地,根据本发明的一实施例的A的R11和R12可以彼此独立地为氢原子、(C1-C20)烷基、(C6-C20)芳基、(C6-C20)芳基(C1-C20)烷基或(C1-C20)烷氧基,可以优选为氢原子或(C1-C20)烷基,具体而言,可以为甲基、乙基、正丙基、异丙基、正丁基、仲丁基、叔丁基或正戊基,a可以为1至3的整数,可以优选为1至2的整数。
优选地,根据本发明的一实施例的D的R13可以为氢原子、(C1-C20)烷基、(C3-C20)环烷基、(C6-C20)芳基、(C6-C20)芳基(C1-C20)烷基、(C1-C20)烷基羰基或(C3-C20)环烷基羰基,作为具体示例,可以为甲基、乙基、正丙基、异丙基、仲丁基或叔丁基、环己基、二环己基甲基、金刚烷基、苯基、苯甲基、甲基羰基、乙基羰基、正丙基羰基、异丙基羰基、叔丁基羰基或金刚烷基羰基,可以优选为甲基、乙基、正丙基、异丙基、仲丁基或叔丁基、环己基、二环己基甲基、金刚烷基、苯基、苯甲基、甲基羰基、乙基羰基、正丙基羰基、异丙基羰基、叔丁基羰基或金刚烷基羰基,可以优选为氢原子或(C1-C20)烷基,作为优选的具体例,可以为甲基、乙基、正丙基、异丙基、仲丁基或叔丁基。
优选地,根据本发明的一实施例,X可以彼此独立地为单(C1-C20)烷基氨基、二(C1-C20)烷基氨基、单(C1-C20)烷基酰胺基、二(C1-C20)烷基酰胺基、(C1-C20)烷基、(C3-C20)杂环烷基或(C1-C20)烷氧基,可以更优选单(C1-C20)烷基氨基、二(C1-C20)烷基氨基、(C1-C20)烷基、(C3-C20)杂环烷基或(C1-C20)烷氧基,作为单(C1-C20)烷基氨基和二(C1-C20)烷基氨基的一个例子,可举出甲基氨基、乙基氨基、正丙基氨基、异丙基氨基、正丁基氨基、仲丁基氨基、叔丁基氨基、异丁基氨基、正己基氨基、正辛基氨基、正癸基氨基、二甲基氨基、二乙基氨基、二正丙基氨基、二异丙基氨基、二正丁基氨基、二仲丁基氨基、二叔丁基氨基、二异丁基氨基、叔丁基异丙基氨基、二正己基氨基、二正辛基氨基、二正癸基氨基,其中优选为二甲基氨基、二乙基氨基或二异丙基氨基,作为(C1-C20)烷基的具体例子,有正丙基、异丙基、正丁基、仲丁基、叔丁基、正戊基、新戊基、正己基、正辛基、正癸基、正十二烷基、正十五烷基或正二十烷基,其中优选为甲基、乙基、异丙基或叔丁基,作为(C3-C20)杂环烷基的具体例子,可以为氮丙啶基、吡咯烷基、哌啶基、氮杂环庚基(azepanyl)或氮杂环辛烷基(azocanyl),可以优选为吡咯烷基或哌啶基,(C1-C20)烷氧基的具体例子,可举出甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、仲丁氧基、叔丁氧基、正戊氧基、新戊氧基、正己氧基、正辛氧基或正十二烷氧基(n-도데속시기),其中优选为甲氧基、乙氧基、异丙氧基或叔丁氧基。
根据本发明的一实施例的过渡金属化合物作为含过渡金属薄膜蒸镀用前体,挥发性高、热稳定性高,从而在得到优良品质的含过渡金属薄膜方面,优选R1至R6彼此独立地为氢原子或(C1-C7)烷基;X可以彼此独立地为单(C1-C20)烷基氨基、二(C1-C20)烷基氨基、(C1-C20)烷基、(C3-C20)杂环烷基或(C1-C20)烷氧基,更优选M为锆、铪、钛;R1至R6彼此独立地为氢原子或(C1-C7)烷基;X可以彼此独立地为二(C1-C20)烷基氨基或(C1-C20)烷氧基。
本发明的由上述化学式1表示的过渡金属化合物可以选自下述化合物,但并不限定于此。
本发明中记载的“烷基”、“烷氧基”以及除此以外包含“烷基”部分的取代基将直链或支链形态均包含,具有1至20个碳原子,优选具有1至10的碳原子,更优选具有1至4的碳原子。
另外,本发明中记载的“芳基”是通过去除一个氢而由芳香族烃衍生的有机基团,包含各个环上适当包含4至7个环原子、优选包含5或6个环原子的单环或稠环系,还包含多个芳基以单键连接的形态。作为具体例子,包含苯、萘、联苯、蒽、茚(indenyl)、芴等,但并不限定于此。
本发明中记载的“环烷基”是指具有3至20个碳原子的非芳香族单环(monocyclic)或多环(multicyclic)系,单环包含环丙基、环丁基、环戊基和环己基,但并不限定于此。作为多环环烷基的例子,包含过氢萘、过氢茚等;桥连的多环环烷基包含金刚烷基和降冰片基等。
本发明中记载的“杂环烷基”是指由碳原子和选自氮、磷、氧和硫中的1至5个杂原子形成的取代或未取代的非芳香族3至15元环基团,杂环烷基基团可以为能够包含稠合、或桥连或螺环系的单环、二环或三环系,并且杂环基团中的氮、磷、碳、氧或硫原子可以根据需要氧化为各种氧化状态。此外,氮原子根据需要可以被季铵化。
本发明提供由下述化学式1表示的过渡金属化合物的制造方法,包括使下述化学式2与化学式3反应而制造由下述化学式1表示的过渡金属化合物的制造步骤。
[化学式1]
[化学式2]
[化学式3]
M(X)4
[上述化学式1至3中,
M为元素周期表中的第4族的过渡金属;
R1至R4彼此独立地为氢原子或(C1-C20)烷基;
R5和R6彼此独立地为氢原子、(C1-C20)烷基、(C6-C20)芳基、(C6-C20)芳基(C1-C20)烷基或(C1-C20)烷氧基;
A为-(CR11R12)a-,R11和R12彼此独立地为氢、(C1-C20)烷基、(C6-C20)芳基、(C6-C20)芳基(C1-C20)烷基或(C1-C20)烷氧基,a为1至3的整数;
D为-N(R13)-,R13为氢原子、(C1-C20)烷基、(C3-C20)环烷基、(C6-C20)芳基、(C6-C20)芳基(C1-C20)烷基、(C1-C20)烷基羰基或(C3-C20)环烷基羰基;
X彼此独立地为(C1-C20)烷基、(C6-C20)芳基、(C6-C20)芳基(C1-C20)烷基、(C1-C20)烷氧基、被(C3-C20)烷基取代或未取代的甲硅烷基、(C3-C20)杂环烷基、被(C1-C20)烷基或(C6-C20)芳基取代或未取代的氨基、被(C1-C20)烷基或(C6-C20)芳基取代或未取代的酰胺基、被(C1-C20)烷基或(C6-C20)芳基取代或未取代的膦基、被(C1-C20)烷基或(C6-C20)芳基取代或未取代的次膦基,其中,X为环戊二烯基衍生物的情况除外;
上述R1至R6、A、D和X的烷基、环烷基、芳基、芳基烷基、烷基羰基、环烷基羰基或烷氧基还可以被(C1-C20)烷基、(C3-C20)环烷基、(C6-C20)芳基或(C6-C20)芳基(C10-C20)烷基取代;
n为1或2的整数。]
根据本发明的一实施例的制造方法还可以包括在使下述化学式4和化学式5反应而制造下述化学式6后,使下述化学式6与下述化学式7反应而制造上述化学式2的步骤。
[化学式4]
[化学式5]
DH2
[化学式6]
[化学式7]
M1-C5H(R1)(R2)(R3)(R4)
[上述化学式4至7中,
M1为碱金属;
R1至R4彼此独立地为氢原子或(C1-C20)烷基;
R5和R6彼此独立地为氢原子、(C1-C20)烷基、(C6-C20)芳基、(C6-C20)芳基(C1-C20)烷基或(C1-C20)烷氧基;
A为-(CR11R12)a-,R11和R12彼此独立地为氢、(C1-C20)烷基、(C6-C20)芳基、(C6-C20)芳基(C1-C20)烷基或(C1-C20)烷氧基,a为1至3的整数;
D为-N(R13)-,R13为氢原子、(C1-C20)烷基、(C3-C20)环烷基、(C6-C20)芳基、(C6-C20)芳基(C1-C20)烷基、(C1-C20)烷基羰基或(C3-C20)环烷基羰基;
上述R1至R6、A和D的烷基、环烷基、芳基、芳基烷基、烷基羰基、环烷基羰基或烷氧基还可以被(C1-C20)烷基、(C3-C20)环烷基、(C6-C20)芳基或(C6-C20)芳基(C10-C20)烷基取代;
X1和X2彼此独立地为卤素基团;
n为1或2的整数。]
根据本发明的一实施例的上述化学式1中,X为杂环烷基的情况下,在制造上述化学式1中X具有单烷基氨基或二烷基氨基的化合物后,可以与杂环烷基(例如与吡咯烷和哌啶)反应而制造。
本发明的制造方法可以由下述反应式1至3表示。
[反应式1]
X2(AX1)SiR5R6+DH2→DH(AX1)SiR5R6
[反应式2]
DH(AX1)SiR5R6+M1Cp→DH(CpA)SiR5R6
[反应式3]
DH(CpA)SiR5R6+Zr(X)4→{D(CpA)SiR5R6}M(X)2
[上述反应式1至3中,A、D、X、M、R5、R6、X1、X2和M1与上述化学式1中的定义相同,CP为环戊二烯。]
本发明的制造方法中使用的溶剂只要是通常的有机溶剂则都可以使用,但优选使用选自己烷、戊烷、二氯甲烷(DCM)、二氯乙烷(DCE)、甲苯(Toluene)、乙腈(MeCN)、硝基甲烷(Nitromethan)、四氢呋喃(THF)、N,N-二甲基甲酰胺(DMF)和N,N-二甲基乙酰胺(DMA)中的1种以上。
反应温度可以为在通常的有机合成中使用的温度,但可以根据反应物质和起始物质的量而不同,优选地,反应式1的反应可以在10至30℃,反应式2的反应可以在55至70℃实施,反应式3的情况下,可以在20至30℃实施,通过NMR等,确认起始物质完全消耗后,使反应完结。当反应完结时,可以在萃取步骤后,减压状态下使溶剂蒸馏后,通过柱层析等通常的方法将目标物分离纯化。
另外,本发明提供包含本发明的过渡金属化合物的含过渡金属薄膜蒸镀用组合物。
优选地,含过渡金属薄膜蒸镀用组合物可仅单独包含本发明的过渡金属化合物作为前体。
本发明的过渡金属化合物如上所述,可以由化学式1表示,优选地,上述化学式1中,M可以为钛、锆或铪。
根据本发明的一实施例的含过渡金属薄膜蒸镀用组合物可以包含以下化合物,该化合物在上述化学式1中,R1至R6和R11至R13彼此独立地为氢原子或(C1-C7)烷基。
另外,根据本发明的一实施例的含过渡金属薄膜蒸镀用组合物可以包含以下化合物,该化合物在上述化学式1中,X彼此独立地为单(C1-C20)烷基氨基、二(C1-C20)烷基氨基、单(C1-C20)烷基酰胺基、二(C1-C20)烷基酰胺基、(C1-C20)烷基或(C1-C20)烷氧基。
优选地,根据本发明的一实施例的含过渡金属薄膜蒸镀用组合物可以只包含用作前体的由上述化学式1表示的过渡金属化合物,在用于蒸镀具有高热稳定性、具有优异的阶梯覆盖性(Step coverage)、高密度的过渡金属薄膜的方面,上述化学式1的过渡金属化合物中,上述R1至R6可以彼此独立地为氢原子或(C1-C7)烷基;X可以彼此独立地为单(C1-C20)烷基氨基、二(C1-C20)烷基氨基、(C1-C20)烷基或(C1-C20)烷氧基。
另外,本发明提供利用包含本发明的过渡金属化合物的含过渡金属薄膜蒸镀用组合物而制造的含过渡金属薄膜。
本发明的含过渡金属薄膜通过利用本发明的包含热稳定性优异、挥发性高的过渡金属化合物作为前体的含过渡金属薄膜蒸镀用组合物,从而能够制造密度高且纯度也高的优良品质的薄膜。
本发明的含过渡金属薄膜可以通过本领域中使用的常规方法制造,作为一个例子,可举出金属有机化学气相沉积法(MOCVD)、原子层沉积法(ALD)工艺、低压化学气相沉积法(LPCVD)、等离子体增强化学气相沉积法(PECVD)或等离子体增强原子层沉积法(PEALD)等。
本发明的含过渡金属薄膜利用本发明的包含过渡金属化合物作为前体的含过渡金属薄膜蒸镀用组合物来制造,作为例子,可以为过渡金属氧化膜、过渡金属氮化膜、过渡金属碳氮化膜或过渡金属硅氮化膜,可以为晶体管的栅极绝缘膜或电容器的介电膜,但并不限定于此。
另外,本发明提供利用本发明的含过渡金属薄膜蒸镀用组合物的含过渡金属薄膜的制造方法。
优选地,本发明的含过渡金属薄膜的制造方法中,作为薄膜蒸镀用前体,可以仅单独使用本发明的过渡金属化合物而制造。
根据本发明的一实施例的含过渡金属薄膜的制造方法,可以根据目标薄膜的结构或热特性来调节蒸镀条件,作为根据本发明的一实施例的蒸镀条件,可举出含有过渡金属化合物的含过渡金属薄膜蒸镀用组合物的投入流量、反应气体、载气的投入流量、压力、射频功率、基板温度等,作为这种蒸镀条件的非限定性例子,含过渡金属薄膜蒸镀用组合物的投入流量为10至1000cc/分钟、载气为10至1000cc/分钟、反应气体的流量为1至1000cc/分钟、压力为0.5至10torr、射频功率为200至1000W、以及基板温度可以在150至400℃范围内进行调节,但并不限定于此。
本发明的含过渡金属薄膜的制造方法中使用的反应气体没有限定,但可以为选自氢气(H2)、肼(N2H4)、臭氧(O3)、氨气(NH3)、氮气(N2)、甲硅烷(SiH4)、硼烷(BH3)、乙硼烷(B2H6)和膦(PH3)中的一种或一种以上的混合气体,载气可以为选自氮气(N2)、氩(Ar)和氦(He)中的一种或两种以上的混合气体。
根据本发明的一实施例的含过渡金属薄膜的制造方法中使用的基板可以为包含Si、Ge、SiGe、GaP、GaAs、SiC、SiGeC、InAs和InP中的一种以上的半导体材料的基板、SOI(硅绝缘体,Silicon On Insulator)基板、石英基板、或显示器用玻璃基板、聚酰亚胺(polyimide)、聚对苯二甲酸乙二醇酯(PET,PolyEthylene Terephthalate)、聚萘二甲酸乙二醇酯(PEN,PolyEthylene Naphthalate)、聚甲基丙烯酸甲酯(PMMA,Poly MethylMethAcrylate)、聚碳酸酯(PC,PolyCarbonate)、聚醚砜(PES)、聚酯(Polyester)等可溶性塑料基板,但并不限定于此。
另外,上述含过渡金属薄膜在上述基板上直接形成薄膜,除此以外,在上述基板与上述含过渡金属薄膜之间可以形成多个导电层、介电层或绝缘层等。
下面,通过实施例对本发明更具体地进行说明。其中,本说明书和权利要求书中使用的用语或单词不能限定地解释为通常或词典中的意思,应基于发明人为了将自己的发明以最佳方法进行说明而能够适当定义用语的概念的原则,解释为符合本发明的技术思想的意思和概念。因此,本说明书中记载的实施例和附图中图示的构成只不过是本发明的最优选的一实施例,并非代表本发明的全部技术思想,因此从本申请初衷来说,应理解为存在能够代替它们的各种等价物和变形例。
[实施例1](C5H4)CH2Si(CH3)2N(CH3)Zr(N(CH3)2)2的合成
ClCH2Si(CH3)2NH(CH3)的合成
在1500ml的戊烷中投入氯(氯甲基)二甲基甲硅烷(228g,1.6mol)后,在-10℃投入甲胺(100g,3.2mol),在常温(25℃)下搅拌24小时。反应完成后过滤去除胺盐后,在减压状态下去除溶剂和挥发性副产物,减压蒸馏而得到了标题化合物197.1g(89.4%)。
1H-NMR(溶剂:苯-d6,ppm)δ2.50(2H,s,ClCH2Si),2.25(3H,d,CH3NH),1.21(1H,m,CH3NH),0.01(6H,s,Si(CH3)2).
(C5H5)CH2Si(CH3)2NH(CH3)的合成
在0℃,在2000ml的四氢呋喃中溶解环戊二烯钠(132.4g,1.5mol)后,在常温(25℃)下投入甲氨基(环戊二烯基甲基)二甲基甲硅烷(197.1g,1.4mmol)后,回流搅拌24小时。结束反应后过滤,去除氯化钠的盐,在减压状态下去除溶剂和挥发性副产物后,减压蒸馏(反应器下部温度基准60℃,0.2torr)而得到了标题化合物75g(31.3%)。
1H-NMR(溶剂:苯-d6,ppm)δ5.81(5H,s,CpCH2Si),2.83(3H,d,CH3NH),1.83(2H,s,CpCH2Si),0.03(6H,s,Si(CH3)2)
(C5H4)CH2Si(CH3)2N(CH3)Zr(N(CH3)2)2的合成
在500ml的戊烷中溶解四(二甲基氨基)锆(80g,0.3mol)后,在0℃投入甲氨基(环戊二烯基甲基)二甲基甲硅烷(50g,0.3mol)后,在常温(25℃)下搅拌24小时。反应结束后,在减压状态下去除溶剂和挥发性副产物后,减压蒸馏(反应器下部温度基准95℃,0.2torr)而得到了标题化合物67g(65%)。
1H-NMR(溶剂:苯-d6,ppm)δ5.83(4H,q,CpCH2Si),3.11(3H,s,CH3N),2.90(12H,s,Zr[N(CH3)2]2),1.99(2H,s,CpCH2Si),0.15(6H,s,Si(CH3)2).
[实施例2]
(C5H4)CH2Si(CH3)2N(CH3)Hf(N(CH3)2)2的合成
在500ml的戊烷中溶解四(二甲基氨基)铪(177g,0.5mol)后,在0℃投入甲氨基(环戊二烯基甲基)二甲基甲硅烷(84g,0.5mol)后,搅拌24小时。反应结束后,在减压状态下去除溶剂和挥发性副产物后,减压蒸馏(反应器下部温度基准130℃,0.3torr)而得到了标题化合物(151)g(70%)。
1H-NMR(溶剂:苯-d6,ppm)δ5.78(4H,q,CpCH2Si),3.09(3H,s,CH3N),2.94(12H,s,Hf[N(CH3)2]2),1.97(2H,s,CpCH2Si),0.13(6H,s,Si(CH3)2).
[实施例3]
(C5H4)CH2Si(CH3)2N(CH3)Ti(N(CH3)2)2的合成
在500ml的戊烷中溶解四(二甲基氨基)钛(112g,0.5mol)后,在0℃投入甲基氨基(环戊二烯基甲基)二甲基甲硅烷(84g,0.5mol)后,搅拌24小时。反应结束后,在减压状态下去除溶剂和挥发性副产物后,减压蒸馏(反应器下部温度基准118℃,0.3torr)而得到了标题化合物(90)g(60%)。
1H-NMR(溶剂:苯-d6,ppm)δ5.70(4H,q,CpCH2Si),3.41(3H,s,CH3N),3.05(12H,s,Ti[N(CH3)2]2),1.94(2H,s,CpCH2Si),0.12(6H,s,Si(CH3)2).
[实施例4](C5H4)CH2Si(CH3)2N(CH2CH2CH3)Zr(N(CH3)2)2的合成
ClCH2Si(CH3)2NH(CH2CH2CH3)的合成
在1000ml戊烷中投入氯(氯甲基)二甲基甲硅烷(109g,0.8mol)后,在-10℃投入正丙胺(90g,1.5mol),在常温(25℃)下搅拌24小时。反应结束后过滤,去除胺盐,在减压状态下去除溶剂和挥发性副产物,减压蒸馏而得到了标题化合物100g(79%)。
1H-NMR(溶剂:苯-d6,ppm)δ2.50(2H,s,ClCH2Si),2.48(2H,t,CH3CH2CH2NH),1.19(2H,m,CH3CH2CH2NH),0.75(3H,t,CH3CH2CH2NH),0.03(6H,s,Si(CH3)2).
(C5H5)CH2Si(CH3)2NH(CH2CH2CH3)的合成
在0℃,在250ml的四氢呋喃中溶解环戊二烯钠(53g,0.6mol)后,在常温(25℃)下投入正丙基氨基(环戊二烯基甲基)二甲基甲硅烷(53g,0.6mol)后,回流搅拌24小时。反应结束后过滤,去除氯化钠的盐,在减压状态下去除溶剂和挥发性副产物后,减压蒸馏(反应器下部温度基准80℃,0.2torr)而得到了标题化合物65g(55%)。
1H-NMR(溶剂:苯-d6,ppm)δ5.81(5H,s,CpCH2Si),2.55(2H,t,CH3CH2CH2NH),1.84(2H,s,CpCH2Si),1.289(2H,m,CH3CH2CH2NH),0.799(3H,t,CH3CH2CH2NH),0.04(6H,s,Si(CH3)2).
(C5H4)CH2Si(CH3)2N(CH2CH2CH3)Zr(N(CH3)2)2的合成
在500ml戊烷中溶解四(二甲基氨基)锆(114g,0.4mol)后,在0℃投入丙基氨基(环戊二烯基甲基)二甲基甲硅烷(83.26g,0.4mol)后,在常温(25℃)下搅拌24小时。反应结束后,在减压状态下去除挥发性副产物后,减压蒸馏(反应器下部温度基准130℃,0.2torr)而得到了标题化合物140g(85%)。
1H-NMR(溶剂:苯-d6,ppm)δ5.84(2H,t,CpCH2Si),5.80(2H,t,CpCH2Si),3.38(2H,t,CH3CH2CH2NH),2.86(12H,s,Zr[N(CH3)2]2),1.99(2H,s,CpCH2Si),1.46(2H,m,CH3CH2CH2NH),0.88(3H,t,CH3CH2CH2NH),0.19(6H,s,Si(CH3)2).
[实施例5]
(C5H4)CH2Si(CH3)2N(CH2CH2CH3)Hf(N(CH3)2)2的合成
在500ml的戊烷中溶解四(二甲基氨基)铪(142g,0.4mol)后,在0℃投入正丙基氨基(环戊二烯基甲基)二甲基甲硅烷(78g,0.4mol)后,搅拌24小时。反应结束后,减压状态下去除溶剂和挥发性副产物后,减压蒸馏(反应器下部温度基准110℃,0.2torr)而得到了标题化合物(120)g(65%)。
1H-NMR(溶剂:苯-d6,ppm)δ5.82(2H,t,CpCH2Si),5.75(2H,t,CpCH2Si),3.33(2H,t,CH3CH2CH2NH),2.90(12H,s,Hf[N(CH3)2]2),1.98(2H,s,CpCH2Si),1.44(2H,m,CH3CH2CH2NH),0.88(3H,t,CH3CH2CH2NH),0.18(6H,s,Si(CH3)2).
[实施例6]
(C5H4)CH2Si(CH3)2N(CH2CH2CH3)Ti(N(CH3)2)2的合成
在500ml的戊烷中溶解四(二甲基氨基)钛(135g,0.6mol)后,在0℃投入正丙基氨基(环戊二烯基甲基)二甲基甲硅烷(117g,0.6mol)后,搅拌24小时。反应结束后,在减压状态下去除溶剂和挥发性副产物后,减压蒸馏(反应器下部温度基准150℃,0.7torr)而得到了标题化合物(118)g(60%)。
1H-NMR(溶剂:苯-d6,ppm)δ5.74(2H,t,CpCH2Si),5.62(2H,t,CpCH2Si),3.62(2H,t,CH3CH2CH2NH),3.01(12H,s,Ti[N(CH3)2]2),1.96(2H,s,CpCH2Si),1.40(2H,m,CH3CH2CH2NH),0.94(3H,t,CH3CH2CH2NH),0.17(6H,s,Si(CH3)2).
[实施例7](C5H4)CH2Si(CH3)2N(CH(CH3)2)Zr(N(CH3)2)2的合成
ClCH2Si(CH3)2NH(CH(CH3)2)的合成
在1000ml的戊烷中投入氯(氯甲基)二甲基甲硅烷(130g,0.9mol)后,在-10℃投入异丙胺(108g,1.8mol),在常温(25℃)下搅拌24小时。反应结束后过滤,去除胺盐,减压状态下去除溶剂和挥发性副产物,减压蒸馏而得到了标题化合物120g(79%)。
1H-NMR(溶剂:苯-d6,ppm)δ2.81(1H,m,(CH3)2CHNH),2.50(2H,s,ClCH2Si),0.89(6H,d,(CH3)2CHNH),0.04(6H,s,Si(CH3)2)
(C5H5)CH2Si(CH3)2NH(CH(CH3)2)的合成
在0℃,在四氢呋喃(250)ml中溶解环戊二烯钠(102g,1.1mol)后,在常温(25℃)下投入异丙基氨基(环戊二烯基甲基)二甲基甲硅烷(184g,1.1mol)后,回流搅拌24小时。结束反应后过滤,去除氯化钠的盐,在减压状态下去除溶剂和挥发性副产物后,减压蒸馏(反应器下部温度基准80℃,0.2torr)而得到了标题化合物(105)g(74%)。
1H-NMR(溶剂:苯-d6,ppm)δ5.97(5H,s,CPCH2Si),2.84(1H,m,(CH3)2CHNH),1.85(2H,s,CpCH2Si),0.94(6H,d,(CH3)2CHNH),0.05(6H,s,Si(CH3)2).
(C5H4)CH2Si(CH3)2N(CH(CH3)2)Zr(N(CH3)2)2的合成
在500ml的戊烷中溶解四(二甲基氨基)锆(144g,0.5mol)后,在0℃投入异丙基氨基(环戊二烯基甲基)二甲基甲硅烷(105g,0.5mol)后,搅拌24小时。反应结束后,在减压状态下去除溶剂和挥发性副产物后,减压蒸馏(反应器下部温度基准130℃,0.2torr)而得到了标题化合物(195)g(94%)。
1H-NMR(溶剂:苯-d6,ppm)δ5.86(2H,t,CpCH2Si),5.78(2H,t,CpCH2Si),4.01(1H,m,(CH3)2CHN),2.84(12H,s,Zr[N(CH3)2]2),1.99(2H,s,CpCH2Si),1.18(6H,d,(CH3)2CHN),0.27(6H,s,Si(CH3)2).
[实施例8](C5H4)CH2Si(CH3)2N(CH2CH2CH3)Zr(NC4H8)2的合成
(C5H4)CH2Si(CH3)2N(CH2CH2CH3)Zr(NC4H8)2的合成
在正丙基氨基(环戊二烯基甲基)二甲基甲硅烷基二甲基氨基锆(35g,90mmol)中,在常温下慢慢投入吡咯烷(13g,181mmol)后,回流搅拌24小时。反应结束后,在减压状态下去除挥发性副产物后,减压蒸馏(反应器下部温度基准172℃,0.2torr)而得到了标题化合物(21)g(53%)。
1H-NMR(溶剂:苯-d6,ppm)δ5.88(2H,d,CpCH2Si),5.86(2H,d,CpCH2Si),3.45(3H,t,CH3CH2CH2N),1.40(2H,m,CH3CH2CH2N),3.38(8H,s,Zr(NC4H8)),2.01(2H,s,CpCH2Si),0.88(2H,t,CH3CH2CH2N),0.20(6H,s,Si(CH3)2).
[实施例9](C5H4)CH2Si(CH3)2N(CH3)Zr(NC4H8)2的合成
(C5H4)CH2Si(CH3)2N(CH3)Zr(NC4H8)2的合成
在甲基氨基(环戊二烯基甲基)二甲基甲硅烷基二甲基氨基锆(17g,47mmol)中,在常温下慢慢投入吡咯烷(6.7g,95mmol)后,回流搅拌24小时。反应结束后,在减压状态下去除挥发性副产物后,减压蒸馏(反应器下部温度基准115℃,0.2torr)而得到了标题化合物15g(38%)。
1H-NMR(溶剂:苯-d6,ppm)δ5.89(2H,d,CpCH2Si),5.85(2H,d,CpCH2Si),3.09(3H,s,CH3N),3.40(8H,s,Zr(NC4H8)),2.00(2H,s,CpCH2Si),0.15(6H,s,Si(CH3)2).
[比较例1](C5H5)Zr(N(CH3)2)3的合成
在3000ml的己烷中添加了2.3M的正丁基锂(520g,1.7mol)。在0℃投入二甲胺(79g,1.7mol)后,在常温(25℃)下搅拌24小时后,在常温(25℃)下加入1000ml的四氢呋喃后,慢慢投入氯化锆(100g,0.4mol)后,搅拌24小时。反应结束后过滤,然后在常温(25℃)下投入裂解的环戊二烯(28g,0.4mol)后,搅拌24小时。反应结束后,在减压状态下去除溶剂和挥发性副产物后,减压蒸馏而得到了标题化合物105g(85%)。
1H-NMR(溶剂:苯-d6,ppm)δ6.03(5H,s,CpZr(N(CH3)2)3),2.89(18H,s,CpZr(N(CH3)2)3)
[实施例10]利用(C5H4)CH2Si(CH3)2N(CH2CH2CH3)Zr(N(CH3)2)2的硅酸锆薄膜的制造
通过原子层沉积法(Atomic layer deposition),在硅基板上制造了硅酸锆薄膜。硅基板维持300℃,将在实施例4中合成的(C5H4)CH2Si(CH3)2N(CH2CH2CH3)Zr(N(CH3)2)2前体填充到不锈钢鼓泡器容器中,维持129℃。首先,以氩气(50sccm)作为载气,将在不锈钢鼓泡器容器内蒸气化的实施例4的前体输送至硅基板,使其吸附于硅基板。其次,利用氩气(4000sccm)去除硅酸锆前体化合物约15秒钟。然后,将约180g/m3的浓度的臭氧气体以500sccm供给10秒而形成硅酸锆薄膜。最后,利用氩气(4000sccm)去除反应副产物和残留反应气体约10秒钟。将如上所述的工序作为一个周期,重复100周期而形成了硅酸锆薄膜。
[实施例11]利用(C5H4)CH2Si(CH3)2N(CH3)Zr(N(CH3)2)2的硅酸锆薄膜的制造
实施例10中,使用在实施例1中合成的前体(C5H4)CH2Si(CH3)2N(CH3)Zr(N(CH3)2)2代替在实施例4中合成的(C5H4)CH2Si(CH3)2N(CH2CH2CH3)Zr(N(CH3)2)2前体,不锈钢鼓泡器容器的温度维持120℃,除此以外,通过与实施例10相同的方法形成了薄膜。
[实施例12]利用(C5H4)CH2Si(CH3)2N(CH3)Hf(N(CH3)2)2的硅酸铪薄膜的制造
通过原子层沉积法(Atomic layer deposition)在硅基板上制造了硅酸铪薄膜。硅基板维持300℃,将在实施例2中合成的(C5H4)CH2Si(CH3)2N(CH3)Hf(N(CH3)2)2前体填充到不锈钢鼓泡器容器中,维持129℃。首先,以氩气(50sccm)作为载气,将在不锈钢鼓泡器容器内蒸气化的硅酸铪前体输送到硅基板,使其吸附于硅基板。其次,利用氩气(4000sccm)去除锡前体化合物约15秒钟。然后,将约180g/m3的浓度的臭氧气体以500sccm供给10秒而形成了硅酸铪薄膜。最后,利用氩气(4000sccm)去除反应副产物和残留反应气体约10秒钟。将如上所述的工序作为一个周期,重复100周期而形成了硅酸铪薄膜。
[实验例1]实施例10至实验例12的过渡金属硅酸盐薄膜组成分析
下述表1中示出了在上述的实施例10至实施例12中蒸镀的薄膜的用X射线光电子能谱分析的组成分析结果。
[表1]
利用实验例1至实验例3蒸镀的薄膜的组成分析结果
如表1所示,可以确认锆、硅、氧的比率为约1:1:4,在没有碳杂质的情况下,硅酸锆(ZrSiO4)或硅酸铪(HfSiO4)以高纯度形成。
另外,如表1所示,本发明的过渡金属化合物通过在一个分子内包含过渡金属和甲硅烷基,从而在将本发明的过渡金属化合物用作前体时形成过渡金属硅酸盐膜,但比较例化合物的情况下只形成过渡金属氧化膜。
[实验例2](C5H4)CH2Si(CH3)2N(CH2CH2CH3)Zr(N(CH3)2)2薄膜的阶梯覆盖特性
为了确认阶梯覆盖特性,利用实施例10中记载的蒸镀方法,在纵横比为约1:6的沟槽晶片上形成硅酸锆薄膜,将其结果示于图1。
如图1所示,可以确认92%以上的高阶梯覆盖特性。
[实验例3]利用(C5H4)CH2Si(CH3)2N(CH3)Zr(N(CH3)2)2的薄膜的阶梯覆盖特性
为了确认阶梯覆盖特性,利用实施例11中记载的蒸镀方法,在纵横比为约1:6的沟槽晶片上形成硅酸锆薄膜,将其结果示于图2。
与图1同样地,图2也能够确认92%以上的高阶梯覆盖特性。
[实验例4](C5H4)CH2Si(CH3)2N(CH3)Hf(N(CH3)2)2薄膜的阶梯覆盖特性
为了确认阶梯覆盖特性,利用实施例12中记载的蒸镀方法,在纵横比为约1:6的沟槽晶片上形成硅酸铪薄膜,将其结果示于图3。
如图3所示,可以确认90%以上的高阶梯覆盖特性。
[实验例5]前体的热稳定性评价
为了对实施例1、4至8和比较例1中制造的前体进行热稳定性评价,用差示扫描量热仪(DSC:Differential Scanning Calorimeter,DSC3,Mettler Toledo)进行测定,将发生热分解的温度示于表2。
[表2]
热稳定性评价
如表2的结果所示,将热分解温度作为DSC的发热起始温度(onset temperature)进行比较,能够确认相对于比较例1的(C5H5)Zr(N(CH3)2)3锆化合物,热稳定性增加,这表明可在更高的温度形成薄膜,能够使精细图案中的阶梯覆盖性增加。
Claims (7)
4.根据权利要求3所述的制造过渡金属化合物的方法,包括使下述化学式4和下述化学式5反应而制造下述化学式6后,使下述化学式6和下述化学式7反应而制造所述化学式2:
化学式4
化学式5
DH2
化学式6
化学式7
M1-C5H(R1)(R2)(R3)(R4)
所述化学式4至7中,
M1为碱金属;
R1至R4彼此独立地为氢原子或C1-C4烷基;
R5和R6彼此独立地为氢原子或C1-C4烷基;
A为-(CR11R12)a-,R11和R12彼此独立地为氢或C1-C4烷基,a为整数1;
D为-N(R13)-,R13为C1-C10烷基;
X彼此独立地为氮丙啶基、吡咯烷基、哌啶基、氮杂环庚烷基或氮杂环辛烷基或二C1-C4烷基氨基;
X1和X2彼此独立地为卤素基团;
n为2的整数。
6.根据权利要求5所述的过渡金属硅酸盐薄膜蒸镀用组合物,其中,所述过渡金属化合物的过渡金属为锆、铪或钛。
7.一种制造过渡金属硅酸盐薄膜的方法,包括向基板添加根据权利要求5所述的组合物。
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0839834A1 (en) * | 1996-10-30 | 1998-05-06 | Repsol Quimica S.A. | Catalyst systems for the polymerization and copolymerization of alpha-olefins |
CN1189504A (zh) * | 1997-01-31 | 1998-08-05 | 赫彻斯特股份公司 | 金属茂催化剂体系的制备方法 |
US6294625B1 (en) * | 1990-03-20 | 2001-09-25 | Exxonmobil Chemical Patents Inc. | Catalyst system of enhanced productivity and its use in polymerization process |
CN102190687A (zh) * | 2010-03-05 | 2011-09-21 | 中国石油天然气股份有限公司 | 一种构型限制碳桥联单茂金属化合物及其制备和应用 |
CN103459405A (zh) * | 2011-03-29 | 2013-12-18 | 住友化学株式会社 | 用于制备过渡金属配合物的方法,用于三聚的催化剂,用于制备1-己烯的方法,用于制备取代的环戊二烯化合物的方法(1) |
CN103930431A (zh) * | 2011-03-15 | 2014-07-16 | 株式会社Mecharonics | 新型第4b族金属有机化合物及其制备 |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE69223035T2 (de) | 1991-10-15 | 1998-05-07 | Dow Chemical Co | Verfahren zur Herstellung von Metall-Koordinationskomplexen |
JP3352374B2 (ja) | 1996-10-30 | 2002-12-03 | レプソル・ケミカ・ソシエダ・アノニマ | アルフアオレフインの重合及び共重合用触媒系 |
KR100714508B1 (ko) * | 1999-12-10 | 2007-05-07 | 다우 글로벌 테크놀로지스 인크. | 치환된 4족 금속 착체, 촉매 및 올레핀 중합 방법 |
KR20060056116A (ko) | 2004-11-19 | 2006-05-24 | 현대자동차주식회사 | 자동변속기의 밸브바디용 세퍼레이팅 플레이트의 체크볼장착구조 |
KR100804413B1 (ko) * | 2006-06-21 | 2008-02-20 | (주)디엔에프 | 지르코늄 산화물 박막 증착용 유기금속 선구물질 및 이의제조 방법 |
US8546276B2 (en) | 2009-07-14 | 2013-10-01 | L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude | Deposition of group IV metal-containing films at high temperature |
KR101284664B1 (ko) | 2010-12-31 | 2013-07-11 | 삼성전자주식회사 | 실릴아민 리간드가 포함된 유기금속화합물, 및 이를 전구체로 이용한 금속 산화물 또는 금속-규소 산화물의 박막 증착 방법 |
KR101263454B1 (ko) * | 2011-03-15 | 2013-11-27 | 주식회사 메카로닉스 | 지르코늄 금속을 함유하는 신규한 유기금속화합물 및 그 제조방법 |
-
2017
- 2017-03-29 KR KR1020170040141A patent/KR101959519B1/ko active IP Right Grant
- 2017-04-06 US US16/093,012 patent/US10913755B2/en active Active
- 2017-04-06 JP JP2018552842A patent/JP6979032B2/ja active Active
- 2017-04-06 EP EP17782612.0A patent/EP3444255A1/en not_active Withdrawn
- 2017-04-06 CN CN201780023511.7A patent/CN109071571B/zh active Active
- 2017-04-12 TW TW106112214A patent/TWI636989B/zh active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6294625B1 (en) * | 1990-03-20 | 2001-09-25 | Exxonmobil Chemical Patents Inc. | Catalyst system of enhanced productivity and its use in polymerization process |
EP0839834A1 (en) * | 1996-10-30 | 1998-05-06 | Repsol Quimica S.A. | Catalyst systems for the polymerization and copolymerization of alpha-olefins |
CN1189504A (zh) * | 1997-01-31 | 1998-08-05 | 赫彻斯特股份公司 | 金属茂催化剂体系的制备方法 |
CN102190687A (zh) * | 2010-03-05 | 2011-09-21 | 中国石油天然气股份有限公司 | 一种构型限制碳桥联单茂金属化合物及其制备和应用 |
CN103930431A (zh) * | 2011-03-15 | 2014-07-16 | 株式会社Mecharonics | 新型第4b族金属有机化合物及其制备 |
CN103459405A (zh) * | 2011-03-29 | 2013-12-18 | 住友化学株式会社 | 用于制备过渡金属配合物的方法,用于三聚的催化剂,用于制备1-己烯的方法,用于制备取代的环戊二烯化合物的方法(1) |
Non-Patent Citations (1)
Title |
---|
Complexes of titanium and zirconium containing a tridentate linked amido-cyclopentadienyl ligand with a soft donor group:synthesis,structure,and ethylene polymerization catalysis;Jun Okuda等,;《Journal of Organometallic Chemistry》;19991231;第127-137页 * |
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JP2019513753A (ja) | 2019-05-30 |
TW201738250A (zh) | 2017-11-01 |
EP3444255A1 (en) | 2019-02-20 |
US10913755B2 (en) | 2021-02-09 |
JP6979032B2 (ja) | 2021-12-08 |
US20190135840A1 (en) | 2019-05-09 |
CN109071571A (zh) | 2018-12-21 |
KR101959519B1 (ko) | 2019-03-18 |
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