TWI401259B - 金屬(iv)四脒鹽化合物以及在氣相沈積中的使用方法 - Google Patents
金屬(iv)四脒鹽化合物以及在氣相沈積中的使用方法 Download PDFInfo
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- TWI401259B TWI401259B TW096123199A TW96123199A TWI401259B TW I401259 B TWI401259 B TW I401259B TW 096123199 A TW096123199 A TW 096123199A TW 96123199 A TW96123199 A TW 96123199A TW I401259 B TWI401259 B TW I401259B
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- metal
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- forming
- compound
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- 229910052751 metal Inorganic materials 0.000 title claims description 70
- 239000002184 metal Substances 0.000 title claims description 70
- 150000001875 compounds Chemical class 0.000 title claims description 31
- 238000007740 vapor deposition Methods 0.000 title description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 53
- 238000000034 method Methods 0.000 claims description 42
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 29
- 229910052726 zirconium Inorganic materials 0.000 claims description 29
- 238000000231 atomic layer deposition Methods 0.000 claims description 23
- 125000000217 alkyl group Chemical group 0.000 claims description 20
- 150000003839 salts Chemical class 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 16
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 16
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 13
- 238000005229 chemical vapour deposition Methods 0.000 claims description 13
- 229910052707 ruthenium Inorganic materials 0.000 claims description 13
- -1 tetrakis salt compound Chemical class 0.000 claims description 13
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 12
- 229910052721 tungsten Inorganic materials 0.000 claims description 12
- 239000010937 tungsten Substances 0.000 claims description 12
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 11
- 229910052750 molybdenum Inorganic materials 0.000 claims description 11
- 239000011733 molybdenum Substances 0.000 claims description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 10
- 229910052770 Uranium Inorganic materials 0.000 claims description 10
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 10
- 229910052735 hafnium Inorganic materials 0.000 claims description 10
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- 229910052718 tin Inorganic materials 0.000 claims description 10
- DNYWZCXLKNTFFI-UHFFFAOYSA-N uranium Chemical compound [U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U] DNYWZCXLKNTFFI-UHFFFAOYSA-N 0.000 claims description 10
- 229910052684 Cerium Inorganic materials 0.000 claims description 9
- 229910052787 antimony Inorganic materials 0.000 claims description 9
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052715 tantalum Inorganic materials 0.000 claims description 9
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 9
- 230000008016 vaporization Effects 0.000 claims description 9
- 229910021529 ammonia Inorganic materials 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 229910052758 niobium Inorganic materials 0.000 claims description 7
- 239000010955 niobium Substances 0.000 claims description 7
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 229910052746 lanthanum Inorganic materials 0.000 claims description 6
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 6
- 150000004767 nitrides Chemical class 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 5
- 229910052797 bismuth Inorganic materials 0.000 claims description 5
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 239000011135 tin Substances 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 5
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 125000000304 alkynyl group Chemical group 0.000 claims description 4
- 125000000392 cycloalkenyl group Chemical group 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- 150000002222 fluorine compounds Chemical class 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 229910052741 iridium Inorganic materials 0.000 claims description 4
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 3
- 229910001882 dioxygen Inorganic materials 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 239000010948 rhodium Substances 0.000 claims description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 3
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 claims description 2
- 229910052776 Thorium Inorganic materials 0.000 claims description 2
- 229910001338 liquidmetal Inorganic materials 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 33
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 32
- 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 22
- 238000006243 chemical reaction Methods 0.000 description 22
- 239000000243 solution Substances 0.000 description 21
- 229910052799 carbon Inorganic materials 0.000 description 20
- 230000015572 biosynthetic process Effects 0.000 description 18
- 238000003786 synthesis reaction Methods 0.000 description 18
- 238000000151 deposition Methods 0.000 description 16
- 239000003446 ligand Substances 0.000 description 16
- 239000002243 precursor Substances 0.000 description 16
- 230000008021 deposition Effects 0.000 description 13
- 239000007788 liquid Substances 0.000 description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 238000001704 evaporation Methods 0.000 description 11
- 230000008020 evaporation Effects 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 10
- 238000002411 thermogravimetry Methods 0.000 description 10
- CRMWDHWPEFVLOU-UHFFFAOYSA-N n,n'-dimethylmethanimidamide Chemical compound CNC=NC CRMWDHWPEFVLOU-UHFFFAOYSA-N 0.000 description 9
- 239000000376 reactant Substances 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 8
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 8
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 8
- 239000006227 byproduct Substances 0.000 description 8
- GVOLZAKHRKGRRM-UHFFFAOYSA-N hafnium(4+) Chemical compound [Hf+4] GVOLZAKHRKGRRM-UHFFFAOYSA-N 0.000 description 8
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 7
- 150000002739 metals Chemical class 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- JMHYNOCZNRXMLN-UHFFFAOYSA-N n,n'-dimethylethanimidamide Chemical compound CNC(C)=NC JMHYNOCZNRXMLN-UHFFFAOYSA-N 0.000 description 7
- RADGOBKLTHEUQO-UHFFFAOYSA-N ruthenium(4+) Chemical compound [Ru+4] RADGOBKLTHEUQO-UHFFFAOYSA-N 0.000 description 7
- 229910007926 ZrCl Inorganic materials 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 238000000859 sublimation Methods 0.000 description 6
- 230000008022 sublimation Effects 0.000 description 6
- 238000006073 displacement reaction Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 150000000703 Cerium Chemical class 0.000 description 4
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 238000005649 metathesis reaction Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 239000012159 carrier gas Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- CIVWZPDBRGONRZ-UHFFFAOYSA-N n,n'-dimethylbutanimidamide Chemical compound CCCC(NC)=NC CIVWZPDBRGONRZ-UHFFFAOYSA-N 0.000 description 3
- 150000002843 nonmetals Chemical group 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000009834 vaporization Methods 0.000 description 3
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 125000003282 alkyl amino group Chemical group 0.000 description 2
- 150000001409 amidines Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 150000001718 carbodiimides Chemical class 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- UHOVQNZJYSORNB-MICDWDOJSA-N deuteriobenzene Chemical compound [2H]C1=CC=CC=C1 UHOVQNZJYSORNB-MICDWDOJSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- WGJJZRVGLPOKQT-UHFFFAOYSA-K lanthanum(3+);trifluoromethanesulfonate Chemical compound [La+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F WGJJZRVGLPOKQT-UHFFFAOYSA-K 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- MJGFBOZCAJSGQW-UHFFFAOYSA-N mercury sodium Chemical compound [Na].[Hg] MJGFBOZCAJSGQW-UHFFFAOYSA-N 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000004377 microelectronic Methods 0.000 description 2
- PPKYHRGDPVUEIW-UHFFFAOYSA-N n,n'-bis(2-methylpropyl)ethanimidamide Chemical compound CC(C)CNC(C)=NCC(C)C PPKYHRGDPVUEIW-UHFFFAOYSA-N 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 150000002825 nitriles Chemical group 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 229910052755 nonmetal Inorganic materials 0.000 description 2
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical group O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 2
- GIDBEKINLBHYLA-UHFFFAOYSA-I pentachlororuthenium Chemical compound Cl[Ru](Cl)(Cl)(Cl)Cl GIDBEKINLBHYLA-UHFFFAOYSA-I 0.000 description 2
- 150000004714 phosphonium salts Chemical class 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229910001023 sodium amalgam Inorganic materials 0.000 description 2
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical group [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- YOUIDGQAIILFBW-UHFFFAOYSA-J tetrachlorotungsten Chemical compound Cl[W](Cl)(Cl)Cl YOUIDGQAIILFBW-UHFFFAOYSA-J 0.000 description 2
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 2
- AHZJKOKFZJYCLG-UHFFFAOYSA-K trifluoromethanesulfonate;ytterbium(3+) Chemical compound [Yb+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F AHZJKOKFZJYCLG-UHFFFAOYSA-K 0.000 description 2
- HNVACBPOIKOMQP-UHFFFAOYSA-N uranium(4+) Chemical compound [U+4] HNVACBPOIKOMQP-UHFFFAOYSA-N 0.000 description 2
- 238000001947 vapour-phase growth Methods 0.000 description 2
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- 238000002424 x-ray crystallography Methods 0.000 description 2
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical class CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 1
- LASVAZQZFYZNPK-UHFFFAOYSA-N 2,4,6-trimethyl-1,3,5-triazine Chemical compound CC1=NC(C)=NC(C)=N1 LASVAZQZFYZNPK-UHFFFAOYSA-N 0.000 description 1
- OQLZINXFSUDMHM-UHFFFAOYSA-N Acetamidine Chemical compound CC(N)=N OQLZINXFSUDMHM-UHFFFAOYSA-N 0.000 description 1
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 description 1
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- 229910001122 Mischmetal Inorganic materials 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- NRJIXZRFIXQKMR-UHFFFAOYSA-N N-methylmethanamine zirconium(4+) Chemical compound CNC.CNC.CNC.CNC.[Zr+4] NRJIXZRFIXQKMR-UHFFFAOYSA-N 0.000 description 1
- 239000012327 Ruthenium complex Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- FKZLAFQXOCKZOC-UHFFFAOYSA-N cerium lithium Chemical compound [Li][Ce] FKZLAFQXOCKZOC-UHFFFAOYSA-N 0.000 description 1
- UTJJFYDIEJAQBS-UHFFFAOYSA-N cerium(3+) cerium(4+) Chemical compound [Ce+3][Ce+4] UTJJFYDIEJAQBS-UHFFFAOYSA-N 0.000 description 1
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 1
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- 238000000576 coating method Methods 0.000 description 1
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- 150000002012 dioxanes Chemical class 0.000 description 1
- 210000005069 ears Anatomy 0.000 description 1
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- 230000003203 everyday effect Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- NKQBQVNKUQULLD-UHFFFAOYSA-N n'-methylethanimidamide Chemical compound CNC(C)=N NKQBQVNKUQULLD-UHFFFAOYSA-N 0.000 description 1
- IHJKBAFLNCXGLC-UHFFFAOYSA-N n,n'-diethylethanimidamide Chemical compound CCNC(C)=NCC IHJKBAFLNCXGLC-UHFFFAOYSA-N 0.000 description 1
- RFJNYMCHBBSSJU-UHFFFAOYSA-N n,n'-dimethylpropanimidamide Chemical compound CCC(NC)=NC RFJNYMCHBBSSJU-UHFFFAOYSA-N 0.000 description 1
- DSWNRHCOGVRDOE-UHFFFAOYSA-N n,n-dimethylmethanimidamide Chemical compound CN(C)C=N DSWNRHCOGVRDOE-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical class [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000000678 plasma activation Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 description 1
- 229910000105 potassium hydride Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000003870 refractory metal Substances 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- MHQWJJLMQJAVBH-UHFFFAOYSA-N ruthenium(5+) Chemical compound [Ru+5] MHQWJJLMQJAVBH-UHFFFAOYSA-N 0.000 description 1
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 159000000008 strontium salts Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical class C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 1
- 235000009657 tetraterpenes Nutrition 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- SYRHIZPPCHMRIT-UHFFFAOYSA-N tin(4+) Chemical compound [Sn+4] SYRHIZPPCHMRIT-UHFFFAOYSA-N 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- 238000005019 vapor deposition process Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- 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
- C07C257/00—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines
- C07C257/10—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines with replacement of the other oxygen atom of the carboxyl group by nitrogen atoms, e.g. amidines
- C07C257/14—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines with replacement of the other oxygen atom of the carboxyl group by nitrogen atoms, e.g. amidines having carbon atoms of amidino groups bound to acyclic carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic Table without C-Metal linkages
-
- 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
- C23C16/04—Coating on selected surface areas, e.g. using masks
- C23C16/045—Coating cavities or hollow spaces, e.g. interior of tubes; Infiltration of porous substrates
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/34—Nitrides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
- C23C16/405—Oxides of refractory metals or yttrium
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- 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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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Chemical Vapour Deposition (AREA)
- Electrodes Of Semiconductors (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本發明是關於含有鍵結於4個脒根配位體(amidinate ligand)之呈+4氧化態之金屬的化合物。本發明亦關於此等化合物作為用於含金屬層的氣相沈積之前驅體的使用方法。
現在使用具有高介電常數之電絕緣性材料(“高k介電質”)來製造電腦記憶體(動態隨機存取記憶體,DRAM)。氧化鋁以及氧化鉭目前在商業上用於DRAM,且正在測試作為替代物之鉿及鋯的氧化物、氮化物以及矽酸鹽以備將來使用。此等高k材料亦可用作微電子元件中之未來電晶體中的絕緣體。
諸如鉭、鎢、鉿、鋯、鈦、鈮及鉬之金屬的導電氮化物具有多種應用及潛在應用,諸如抵擋銅擴散之障壁以及作為微電子元件中之電容器及電晶體的電極。此等耐高溫(refractory)金屬亦可用作銅之黏著促進層,以及作為電極或電內連線。
氣相沈積是製造此等材料之較佳方法。氣相沈積是包含化學氣相沈積(chemical vapor deposition,CVD)以及原子層沈積(atomic layer deposition,ALD)的通用術語。在CVD方法中,將一或多種蒸氣傳遞至固體材料於其上沈積之表面;藉由諸如加熱、光照或電激發(電漿活化)之方法來起始使蒸氣轉化成固體之化學反應。在ALD方法中,將兩種或兩種以上蒸氣交替傳遞至表面,於所述表面上發生反應而沈積固體產物。ALD能夠在現代DRAM之極狹窄的結構內部沈積此等材料。CVD通常提供比ALD高的沈積速率,但在極狹窄孔內部之沈積均一性較低。
用於氣相沈積的合格前驅體必須是揮發性、熱穩定以及高反應性的。識別滿足所有此等複雜要求的化合物是困難的。尚未知諸如鉿、鋯、鉭、鈮、鎢、鉬、錫、碲及鈾之金屬的完全令人滿意之前驅體。諸如ZrCl4
、HfCl4
及TaCl5
之鹵化物在一些基板表面上成核困難,且副產物鹽酸阻礙狹窄孔內部之完全共形沈積。烷氧化物(alkoxide)及二烷基醯胺(dialkylamide)之熱穩定性低於最佳熱穩定性。有機金屬化合物可能缺乏適合的反應性,而使碳作為雜質留在膜中。因此,需要此等金屬之具大揮發性、熱穩定以及高反應性的來源。
本發明之一態樣包括含有鍵結於4個脒根配位體(amidinate ligand)之呈+4氧化態之金屬的化合物。在較佳實施例中,此等配位體包含N,N'
-二烷基脒根配位體。較佳金屬包括鉿、鋯、鉭、鈮、鎢、鉬、錫、碲及鈾。
在一或多個實施例中,化合物具有結構式
其中M為呈+4氧化態之金屬,且R1
至R12
之各者獨立地選自由氫、烴基、經取代烴基以及其他非金屬原子之基團組成之群。
在一或多個實施例中,烴基是選自由烷基、環烷基、烯基、環烯基、炔基及環炔基以及由烴之氟化物衍生物組成之經取代烴基組成之群,或包含非金屬原子之基圍是選自由烷基矽烷基以及烷基胺基組成之群。
在一或多個實施例中,金屬M是選自由鋯、鉿、錫、鉭、鈮、鎢、鉬、鈾、錸、鉑、鋨、銥、釕、鈀、鈦、銠、釩、鈰及鉛組成之群,或金屬M是選自由鉿、鋯、鉭、鈮、鎢、鉬、錫、碲及鈾組成之群。
在一或多個實施例中,R1
至R12
之至少一者為具有5個或更少碳之低級烷基(lower alkyl)。
在一或多個實施例中,R1
至R12
是選自由具有5個或更少碳以及氫之低級烷基組成之群。
在一或多個實施例中,R1
、R3
、R4
、R6
、R7
、R9
、R10
及R12
為在α-位置無分枝之烷基。
本發明之另一態樣包括一種使用根據本發明之一或多個實施例之化合物沈積包含金屬之膜之方法。所述方法包括使受熱表面暴露於一或多種揮發性金屬四脒鹽化合物之蒸氣。例示性沈積方法包括化學氣相沈積(CVD)及原子層沈積(ALD)。
在一或多個實施例中,所述方法包括使基板暴露於氧來源,且薄膜包含金屬氧化物。
在一或多個實施例中,氧來源包含水蒸汽或分子氧(dioxygen)或臭氧。
在一或多個實施例中,所述方法包括使基板暴露於氮來源,且薄膜包含金屬氮化物。
在一或多個實施例中,氮來源包含氨。
在一或多個實施例中,蒸氣是藉由汽化固體金屬四脒鹽化合物,或藉由汽化液體金屬四脒鹽化合物而獲得。
在一或多個實施例中,蒸氣是藉由在100℃至250℃之範圍內的溫度下汽化金屬四脒鹽而獲得。
在一或多個實施例中,表面是處於約200℃至500℃之範圍內的溫度下。
本發明提供適用於氣相沈積方法(包括化學氣相沈積以及原子層沈積)之熱穩定、揮發性金屬化合物。
較佳化合物包括揮發性金屬(IV)四(N,N'
-二烷基脒鹽)錯合物。通常,此等化合物可由單體式1來描述,
其中M為呈+4氧化態之金屬,且R1
至R12
(例如Rn
,其中n=1-12)可獨立地選自氫,諸如烷基、環烷基、烯基、環烯基、炔基及環炔基之烴基及其氟化物衍生物,或諸如烷基矽烷基及烷基胺基之其他包含非金屬原子之基團。除非另外說明,否則提及Rn
同樣適用於R1
至R12
之各者。
在一或多個實施例中,Rn
為含有5個或更少碳之低級烷基。在一或多個實施例中,Rn
為氫與低級烷基之混合物。在較佳實施例中,Rn
是選自包含甲基、乙基以及正丙基之群。此等小烷基是較佳的,因為其足夠小而適合具有極穩定螯合鍵結之結構1。在一或多個實施例中,R1
、R3
、R4
、R6
、R7
、R9
、R10
或R12
中之一或多者為無分枝α-碳之烴基。如本文中所使用,α-碳為直接結合於脒根配位體之一個氮之碳。諸如異丙基、第二丁基或第三丁基之在α-碳處分枝之烷基較為不佳,因為其可能引起過度擁擠而不適合結構1。因此,支鏈烷基通常將提供穩定性較低之金屬脒鹽。儘管如此,根據一或多個實施例仍涵蓋支鏈基團,尤其是在使用較大金屬中心或在α-碳以外存在分枝之情況下。
可用於本發明之一或多個實施例中之例示性四價金屬包括鋯、鉿、錫、鉭、鈮、鎢、鉬、鈾、錸、鉑、鋨、銥、釕、鈀、鈦、銠、釩、鈰、碲以及鉛。具有相對較大離子半徑之四價金屬離子形成尤其穩定的四脒鹽錯合物,彼等金屬包括鋯、鉿、錫、鉭、鈮、鎢、鉬、碲以及鈾。可形成四脒鹽之具有相對較小離子半徑之四價金屬離子包括錸、鉑、鋨、銥、釕、鈀、鈦、銠以及釩。
在一或多個實施例中,脒根配位體是對稱的,例如式1中之諸如R1
與R3
或R4
與R6
等之N-結合R基團是相同的。在一或多個實施例中,脒根配位體是不對稱的,例如式1中之R1
與R3
是不同的。在兩種實施例之中,式1中之例如R2
之碳結合R基團可相同或不同。
在一或多個實施例中,金屬四(N,N'
-二烷基脒鹽)化合物是使用N,N'
-二烷基脒來製備。對稱性脒可藉由三氟甲烷磺酸鑭(lanthanum trifluoromethanesulfonate)(亦稱為三氟甲磺酸鑭(lanthanum triflate)),即La(CF3
SO3
)3
,催化之胺與腈的縮合而形成:
使其中R1
為諸如正丙基、正丁基或異丁基之在α-位置處無分枝之烷基的胺在回流溫度(reflux temperature)下,在幾小時至幾天內反應。其中R1
為甲基或乙基之胺具有使得其必須在反應期間限制在壓力容器內之揮發性。在反應過程期間,副產物氨可經由背壓調節器(back-pressure regulator)自壓力容器釋放。完全反應在室溫下耗時幾天,或在較高溫度及壓力下耗時較短時期。用於此反應之較為廉價之催化劑可自天然存在之金屬鑭混合物(“混合稀土金屬(misch metal)”)之混合三氟甲磺酸鹽製得。
不對稱性脒可根據以下反應製備:
金屬脒鹽可藉由交換反應製備,其中使金屬二烷基醯胺與脒反應。或者,可藉由使脒與丁基鋰或與胺基鈉或與氫化鉀反應而將脒轉化成其鹼金屬鹽。隨後可使鹼金屬脒鹽與金屬氯化物經歷鹽置換反應(salt metathesis reaction)以形成金屬脒鹽。形成鋰脒鹽之更常用的方法為使碳化二醯亞胺(carbodiimide)與烷基鋰反應。此習知合成途徑在R1
及R3
烷基為在α-位置處分枝之烷基時是更為有效,因為相應之碳化二醯亞胺更為穩定。
金屬四脒鹽化合物可用以在氣相沈積方法中形成含金屬膜。根據一或多個實施例之化合物之蒸氣可用以沈積諸如金屬、金屬氧化物、金屬氮化物、金屬氮氧化物、金屬硫化物及其類似物之材料。此等氣相沈積方法包括CVD及ALD。在CVD中,將金屬四脒鹽之蒸氣視情況與共反應物氣體或蒸氣一起供應至表面。在ALD中,以交替時間週期將金屬四脒鹽之蒸氣與共反應物供應至表面。CVD處理描述於(例如)以引用之方式併入本文之美國專利5,139,999以及Hugh O.Pierson之“Handbook of Chemical Vapor Deposition:Principles,Technology and Applications”(第2版,Noyes Publications,1999)中。ALD處理描述於以引用之方式併入本文之美國專利6,969,539以及Handbook of Thin Film Materials(H.Nalwa編,Academic Press,2002)之第1卷,第103頁上之M.Ritala及M.Leskela的論文“Atomic Layer Deposition”中。氧化物可使用諸如水蒸氣、分子氧、臭氧、過氧化氫以及醇或自含氧氣體或蒸氣形成之電漿的共反應物來形成。氮化物可使用諸如氨、肼(hydrazine)或自含氮氣體或蒸氣形成之電漿的共反應物來形成。硫化物可使用諸如硫化氫或自含硫氣體或蒸氣形成之電漿的共反應物來形成。用於進行ALD之設備示意性展示於圖1之橫截面中。在ALD方法操作期間,諸如氮氣之載氣自來源91及92連續地流過沈積室110進入管道(pipe)150到達收集器(trap)及真空泵(vacuum pump)。四脒鹽前驅體21保留在容器11中,容器11在烘箱41中經加熱至足以使四脒鹽前驅體形成蒸氣31之溫度。四價脒鹽前驅體之蒸氣31在閥門51打開時流入烘箱81中之真空室61中。隨後關閉閥門51且打開閥門71,以使前驅體蒸氣之等分試樣流經加熱爐120內部之基板130。隨後關閉閥門71且歷經允許過量未反應之前驅體與揮發性反應副產物一起自腔室110清除之時間。將諸如水或氨之第二試劑22置放於通常保持在室溫下之容器12中,容器12位於烘箱42中。藉由打開閥門52使第二試劑之蒸氣32流入位於烘箱82中的蒸氣空間62,隨後將閥門52關閉。打開閥門72,以使第二試劑之等分試樣流入沈積室110中。隨後關閉閥門72且歷經允許未反應之過量第二試劑與揮發性反應副產物一起自沈積室110清除之時間。隨後重複此操作循環,以在基板130上累積所要塗層厚度。
用於進行CVD之設備包括許多相似特徵。設備可包括容納四脒鹽前驅體之容器,所述容器經加熱至使四脒鹽前驅體形成蒸氣之溫度。四脒鹽前驅體蒸氣自容器流出且流入容納基板之加熱爐中。可將額外的共反應物蒸氣與四脒鹽前驅體一起引入加熱爐中,或可在四脒鹽蒸氣暴露於受熱基板之前將共反應物蒸氣與四脒鹽蒸氣預混合。排氣系統自爐中移除副產物以及未反應之反應物。
四脒鹽前驅體可以純液體,適當溶劑中之溶液之形式,或以固體形式使用。適合之沈積條件(諸如汽化及沈積之溫度、壓力、流動速率以及共反應物)可容易地由熟習此項技術者來確定。例示性ALD及CVD條件包括200至500℃且更佳300至400℃之基板溫度,0.1至10托且更佳1至5托之範圍內之蒸氣壓,約100至250℃且更佳150至200℃之汽化溫度,1至100毫微莫耳/平方公分沈積表面且更佳2至20毫微莫耳/平方公分之ALD劑量,以及0.01托-秒至10托-秒且更佳0.1至1托-秒之ALD暴露量。涵蓋具有高縱橫比之特徵所需之ALD暴露量大致隨縱橫比之平方而增加。
實例1.N,N' -二-異丁基乙脒之合成
在氮環境下,將異丁胺(7.3 g,0.1 mol)、乙腈(4.1 g,0.1 mol)及三氟甲磺酸鑭(即La(CF3
SO3
)3
)(1.2 g,0.002 mol)之溶液回流30小時。藉由在40℃約0.2托下分餾移除未反應之起始物質及副產物2,4,6-三甲基-1,3,5-三嗪。隨後在95℃及0.06托下蒸餾無色之N,N'
-二-異丁基乙脒。藉由第二次蒸餾進行進一步純化。產量:6.4 g(以異丁胺計75%)。1
H NMR(苯-d 6
+少量CD3
OD,ppm):3.1(d,4,NCH 2
),1.9(m,2,CH
(C
H3
)2
),1.7(s,3,CCH 3
),1.0(d,12,CH(CH 3
)2
)。
實例2. 四(N,N' -二-異丁基乙脒根基)鋯(IV)(即Zr( i Bu-AMD) 4 )之合成
將0.8 g(3 mmol)四(二甲基醯胺基)鋯(IV)(即Zr(NMe2
)4
)溶於10 mL甲苯中且隨後冷卻至-30℃歷時30分鐘。向此溶液中添加2.3 g(13.5 mmol)N,N'
-二-異丁基乙脒(即 i
Bu-AMD),且在90℃下將混合物加熱隔夜(配位體交換反應)。冷卻至-30℃後,無色結晶物質沈澱且將其濾出。產量:1.85 g(80%)。1
H NMR(苯-d 6
,ppm):3.10(d,16,J
=6.9 Hz,NCH 2
),1.89(m,8,CH
(CH3
)2
),1.71(s,12,CCH 3
),1.00(d,48,J
=6.6 Hz,d,CH(CH 3
)2
)。13
C NMR(苯-d 6
,ppm):174(C
CH3
),55.76(NC
H2
),31.74(C
H(CH3
)2
),21.134(CH(C
H3
)2
,12.10(CC
H3
)。C40
H84
N8
Zr之分析計算值:C 62.53,H 11.02,N 14.58。實驗值:C 62.76,H 11.25,N 14.50。
使用X射線結晶學測定四(N,N'
-二-異丁基乙脒根基)鋯(IV)之分子結構,展示於圖2中,其中原子由50%熱橢圓體表示且為清晰起見而省略氫原子。各分子含有一個由4個脒根配位體之8個氮原子圍繞之鋯原子。
在熱解重量分析(TG)期間產物蒸發一半時之溫度(即T1/2
)為240℃,所述溫度是在大氣壓下流動氮氣中量測。此TG實驗亦證明化合物具有高熱穩定性且完全汽化(殘餘物可忽略)。
實例3.四(N,N' -二-異丁基乙脒根基)鉿(IV)(即Hf( i Bu-AMD) 4 )之合成
此化合物以類似於實例2中關於Zr( i
Bu-AMD)4
所述之方式,自3 mmol四(二甲基醯胺基)鉿(IV)(即Hf(NMe2
)4
)起始來製備。產物以白色粉末形式分離。產量:2.17 g(85%)。1
H NMR(苯-d 6
,ppm):3.15(d,16,J
=7.2 Hz,NCH 2
),1.87(m,8,CH
(CH3
)2
),1.70(s,12,CCH 3
),0.99(d,48,J
=6.8 Hz,CH(CH 3
)2
)。C40
H84
HfN8
之分析計算值:C 56.15,H 9.90,N 13.10。實驗值:55.85,H 9.77,N 13.30。
此鉿錯合物之TG性質類似於實例2中描述之鋯錯合物之TG性質。
實例4.N.N' -二甲基乙脒及其鋰鹽之合成
將無水三氟甲磺酸鑭(3.00 g,5.12 mmol)置放於壓力容器中。將無水乙腈(23.3 g,0.568 mol)冷凝至冷容器中。用液氮冷卻容器且添加無水甲胺(53.1 g,1.71 mol)。密封容器且使其升溫至室溫。每天釋放副產物氨氣。反應通常在3天後完成。隨後,藉由在20℃及0.04托下昇華移除副產物N-甲基乙脒分離出無色之N,N'
-二甲基乙脒。1
H NMR(苯-d 6
,ppm):2.60(s,6,NCH 3
),1.40(s,3,CCH 3
)。
N,N'
-二甲基乙脒之鋰鹽藉由將1體積之N,N'
-二甲基乙脒溶於5體積之無水乙醚中且將溶液冷卻至-78℃來製備。緩慢添加溶於己烷中之等莫耳量之丁基鋰,同時攪拌。使反應混合物升溫至室溫。減壓移除乙醚以及戊烷。隨後,將白色固體殘餘物溶於無水二噁烷中。N,N'
-二甲基乙脒根基-鋰於二噁烷中之所得溶液用於一些以下實例。
實例5. 四(N,N' -二甲基乙脒根基)鋯(IV)之合成
此化合物藉由配位體交換以類似於實例2中關於Zr( i
Bu-AMD)4
所述之方式,使用N,N'
-二甲基乙脒替代N,N'
-二-異丁基乙脒來製備。或者,使ZrCl4
與溶於二噁烷中之N,N'
-二甲基乙脒之鋰鹽反應(鹽置換反應)。將此反應混合物加熱至回流歷時8小時。蒸發二噁烷後,用戊烷萃取固體殘餘物。在傾析懸浮液以移除所沈澱之氯化鋰後,減壓蒸發戊烷以得到粗產物,隨後藉由在60℃及40毫巴之壓力下昇華來純化粗產物。亦可在大氣壓下在160℃下使粗產物昇華。當以小規模進行合成時,昇華後之產率為24%。1
H NMR(苯-d 6
,ppm):3.03(s,24,NCH 3
),1.57(s,12,CCH 3
)。13
C NMR(苯-d 6
,ppm):175.99(s,C
CH3
),34.55(s,NC
H3
),9.84(s,CCH3
)。C16
H36
N8
Zr分析計算值:C 44.51,H 8.40,N 25.95。實驗值:C 45.31,H 7.92,N 25.60,或在第二次分析中為C 43.30,H 8.76,N 24.87。此產物比實例2之產物四(N,N'
-二-異丁基乙脒根基)鋯(IV)更具揮發性,因為其來自TG曲線之T1/2
值為216℃,並具有0.6%殘餘物。其熔點為約168℃。
實例6. 四(N,N' -二甲基乙脒根基)鉿(IV)之合成
此化合物藉由實例5中描述之鹽置換反應自HfCl4
製備。1
H NMR(苯-d 6
,ppm):3.07(s,24,NCH 3
),1.55(s,12,CCH 3
)。13
C NMR(苯-d 6
,ppm):175.69(s,C
CH3
),34.31(s,NC
H3
),10.09(s,CC
H3
)。C16
H36
HfN8
之分析計算值:C 37.03,H 6.99,N 21.59。實驗值:37.00,H 6.89,N 21.34。此產物比實例3之產物四(N,N'
-二-異丁基乙脒根基)鉿(IV)更具揮發性,因為其來自TG曲線之T1/2
值為221℃。其蒸發後之殘餘物可忽略,即小於1%,且其熔點為約171℃。
實例7. 四(N,N' -二甲基丙脒根基)鋯(IV)之合成
藉由實例4中描述之方法使用丙腈替代乙腈來製備鋰N,N'
-二甲基丙脒鹽之二噁烷溶液。隨後將此溶液與ZrCl4
一起用於實例5中描述之鹽置換方法中以製備四(N,N'
-二甲基丙脒根基)鋯(IV)。此化合物亦可藉由類似於實例2中所述之配位體交換反應來製備。1
H NMR(苯-d 6
,ppm):3.07(s,24,NCH 3
),2.10(q,8,J
=7.6 Hz,CH 2
CH3
),0.96(t,12,J
=7.6 Hz,CH2
CH 3
)。13
C NMR(苯-d 6
,ppm):180.12(s,C
CH2
CH3
),33.92(s,NC
H3
),17.31(s,CCH2 C
H3
),10.41(s,CC
H2
CH3
)。C20
H44
N8
Zr之分析計算值:C 49.24,H 9.09,N 22.97。實驗值:49.42,H 9.04,N 22.43。其熔點為109℃,此熔點足夠低而使其在鼓泡器中在足夠高以致可汽化之溫度下為液體。其來自TG曲線之T1/2
值為245℃,並具有0.6%之可忽略殘餘物。
實例8. 四(N,N' -二甲基丙脒根基)鉿(IV)之合成
此化合物藉由實例7中描述之鹽置換反應自HfCl4
製備。其亦可藉由類似於實例1中所述之配位體交換反應來製備。1
H NMR(苯-d 6
,ppm):3.10(s,24,NCH 3
),2.08(q,8,J
=7.6 Hz,CH 2
CH3
),0.95(t,12,J
=7.6 Hz,CH2
CH 3
)。13
C NMR(苯-d 6
,ppm):179.75(s,C
CH2
CH3
),33.71(s,NC
H3
),17.51(s,CCH2 C
H3
),10.40(s,CC
H2
CH3
)。C20
H44
HfN8
之分析計算值:C 41.77,H 7.71,N 19.48。實驗值:42.32,H 8.11,N 19.18。其熔點為114℃,此熔點足夠低而使其在鼓泡器中在足夠高以致可汽化之溫度下為液體。其來自TG曲線之T1/2
值為252℃,並具可忽略之非揮發性殘餘物。使用X射線結晶學測定四(N,N'-二甲基丙脒根基)鉿(IV)之分子結構,展示於圖3中,其中原子由50%熱橢圓體表示且為清晰起見省略氫原子。各分子含有一個由4個脒根配位體之8個氮原子圍繞之鉿原子。
實例9. 四(N,N' -二甲基丁脒根基)鋯(IV)之合成
藉由實例4中描述之方法使用丁腈替代乙腈來製備鋰N,N'
-二甲基丁脒鹽之二噁烷溶液。隨後將此溶液與ZrCl4
一起用於實例5中描述之鹽置換方法中以製備四(N,N'
-二甲基丁脒根基)鋯(IV)。此化合物亦可藉由類似於實例1中所述之配位體交換反應來製備。此化合物在室溫下為液體,因此藉由蒸餾而非昇華來純化。1
H NMR(苯-d 6
,ppm):3.11(s,24,NCH 3
),2.15(t,8,J
=8.0 Hz,CCH 2
CH2
CH3
),1.49(m,8,CCH2
CH 2
CH3
),0.90(t,12,J
=6.8 Hz,CCH2
CH2
CH 3
)。13
C NMR(苯-d 6
,ppm):179.27(s,C
CH2
CH2
CH3
),34.28(s,NC
H3
),26.14(s,CCH2 C
H2
CH3
),19.82(s,CCH2
CH2 C
H3
),14.47(s,CC
H2
CH2
CH3
)。C24
H52
N8
Zr之分析計算值:C 52.99,H 9.63,N 20.60。實驗值:53.63,H 9.87,N 20.89。其T1/2
值為246℃且蒸發後留下可忽略之殘餘物。
實例10. 四(N,N' -二甲基丁脒根基)鉿(IV)之合成
此化合物藉由實例9中描述之鹽置換反應自HfCl4
製備。其亦可藉由類似於實例1中所述之配位體交換反應來製備。此化合物在室溫下為液體,因此藉由蒸餾而非昇華來純化。1
H NMR(苯-d 6
,ppm):3.15(s,24,NCH 3
),2.13(t,8,J
=8.0 Hz,CCH 2
CH2
CH3
),1.49(m,8,CCH2
CH 2
CH3
),0.89(t,12,J
=6.8 Hz,CCH2
CH2
CH 3
)。13
C NMR(苯-d 6
,ppm):178.87(s,C
CH2
CH2
CH3
),34.08(s,NC
H3
),26.29(s,CCH2 C
H2
CH3
),19.82(s,CCH2
CH2 C
H3
),14.41(s,CC
H2
CH2
CH3
)。C24
H52
HfN8
之分析計算值:C 45.67,H 8.30,N 17.75。實驗值:45.31,H 8.81,N 17.61。其T1/2
值為252℃且蒸發後留下可忽略之殘餘物。
實例11. 四(N,N' -二乙基乙脒根基)鋯(IV)之合成
藉由實例4中描述之方法使用乙胺替代甲胺來製備鋰N,N'
-二乙基乙脒鹽之二噁烷溶液。隨後將此溶液與ZrCl4
一起用於實例5中描述之鹽置換方法中以製備四(N,N'
-二乙基乙脒根基)鋯(IV)。其亦可藉由類似於實例1中所述之配位體交換反應來製備。1
H NMR(苯-d 6
,ppm):3.32(q,16,J
=7.2 Hz,NCH 2
CH3
),1.63(s,12,CCH 3
),1.10(t,24,J
=7.2 Hz,NCH2
CH 3
)。13
C NMR(苯-d 6
,ppm):173.59(s,C
CH3
),41.38(s,NC
H2
CH3
),18.00(s,NCH2 C
H3
),10.20(s,CCH3
)。C24
H52
N8
Zr之分析計算值:C 52.99,H 9.63,N 20.60。實驗值:52.86,H 9.40,N 20.99。其T1/2
值為242℃且蒸發後留下可忽略之殘餘物。
實例12. 四(N,N' -二乙基乙脒根基)鉿(IV)之合成
此化合物藉由實例11中描述之鹽置換方法自HfCl4
製備。其亦可藉由類似於實例1中所述之配位體交換反應來製備。1
H NMR(苯-d 6
,ppm):3.32(q,16,J
=7.2 Hz,NCH 2
CH3
),1.63(s,12,CCH 3
),1.10(t,24,J
=7.2 Hz,NCH2
CH 3
)。13
C NMR(苯-d 6
,ppm):173.07(s,C
CH3
),41.08(s,NC
H2
CH3
),18.00(s,NCH2 C
H3
),10.59(s,CC
H3
)。C24
H52
N8
Hf之分析計算值:C 45.67,H 8.30,N 17.75。實驗值:46.17,H 7.93,N 17.27。其T1/2
值為264℃且蒸發後留下可忽略之殘餘物。
實例13. 四(N,N' -二乙基乙脒根基)鉭(IV)之合成
此化合物以兩個步驟自五氯化鉭製備。第一步涉及在氮氣下-78℃下將五氯化鉭之乙醚溶液(0.95 mmol,331 mg於20 mL乙醚中)添加至鋰N,N'
-二乙基乙脒鹽之溶液中(2 mmol於20 mL乙醚中,自脒及正丁基鋰之己烷溶液(2.6 M)原位製備)。暫描述為參氯-雙(N,N'
-二乙基乙脒根基)鉭(V)之中間物可部分溶於乙醚中而得到橙色溶液。添加一些二噁烷以幫助溶解中間物,且在室溫下再添加兩當量之鋰N,N'
-二乙基乙脒鹽(2 mmol於20 mL乙醚中,自脒及正丁基鋰之己烷溶液(2.6 M)原位製備)。亦添加1當量之鈉汞齊(22.8 mg於3.53 g具有0.645重量%鈉之汞齊中)。在室溫下將溶液攪拌隔夜。溶液在12小時內變成暗紫色。真空汽提乙醚,且添加戊烷(20 mL)。傾析紫色溶液且將其與汞及不溶性物質分離。將其真空乾燥且得到產物,一種紫色固體,此產物可暫描述為四(N,N'
-二乙基乙脒根基)鉭(IV)。產物可在真空下昇華,且昇華餾份亦可在150℃下0.01 mmHg之壓力下再次昇華而無分解。儘管產物含有雜質,但是其顏色及其可在真空下昇華而無分解之事實指示其可能為揮發性鉭(IV)脒鹽。
實例14. 其他金屬(IV)四脒鹽之合成
含有其他金屬中心之化合物可以類似於實例3中所述之方式,藉由使用適合金屬來源替代ZrCl4
來製備。舉例而言,四(N,N'
-二甲基乙脒根基)鎢(IV)可使用氯化鎢(IV)(即WCl4
)來製備;四(N,N'
-二甲基乙脒根基)錫(IV)可使用氯化錫(IV)(即SnCl4
)來製備;四(N,N'
-二甲基乙脒根基)碲(IV)可自TeCl4
來製備;並且四(N.N'
-二甲基乙脒根基)鈾(IV)可使用氯化鈾(IV)(即UCl4
)來製備。
實例15. 自四(N,N' -二甲基丁脒根基)鉿(IV)及臭氧原子層沈積氧化鉿
以10托-秒之暴露量自200℃之直接液體注射系統將10毫微莫耳/平方公分劑量的四(N,N'
-二甲基丁
脒根基)鉿(IV)之蒸氣引入400℃之ALD反應器中,交替地以10托-秒之暴露量引入20毫微莫耳/平方公分劑量之臭氧。氧化鉿之膜以80:1之高縱橫比共形沈積於狹窄孔內部。
實例16. 自四(N,N' -二甲基丁脒根基)鉿(IV)及水蒸汽原子層沈積氧化鉿
以10托-秒之暴露量自200℃之直接液體注射系統將10毫微莫耳/平方公分劑量的四(N,N'
-二甲基丁
脒根基)鉿(IV)之蒸氣引入400℃之ALD反應器中,交替地以10托-秒之暴露量引入20毫微莫耳/平方公分劑量之水蒸汽。氧化鉿之膜以80:1之高縱橫比共形沈積於狹窄孔內部。
實例17. 自四(N,N' -二甲基丁脒根基)鉿(IV)及氨原子層沈積氮化鉿
以10托-秒之暴露量自200℃之直接液體注射系統將10毫微莫耳/平方公分劑量的四(N,N'
-二甲基丁
脒根基)鉿(IV)之蒸氣引入400℃之ALD反應器中,交替地以10托-秒之暴露量引入20毫微莫耳/平方公分劑量之氨。氮化鉿之膜以80:1之高縱橫比共形沈積於狹窄孔內部。
實例18.N,N' -二甲基甲脒之合成
在-196℃下,在封閉壓力容器中,將過量之無水甲胺(39 g,1.26 mol)冷凝於無水氰化鈉(30.2 g,0.617 mol)、無水鹽酸甲胺(41.6 g,0.617 mol)與三氟甲磺酸鑭(5.2 g,8.88 mmol)之混合物上。使混合物升溫至室溫且隨後在40-50℃下超音波處理72小時。在室溫下使揮發性氣體逸出反應容器,且將無水甲胺(10 g,0.322 mol)冷凝於經冷卻之反應混合物上,再重複兩次此蒸發、添加甲胺及超音波處理之循環。最後藉由在室溫下將反應容器緩慢通氣而釋放所有揮發物。添加乙醚(50 mL)且在氮氣下將反應混合物傾入大燒瓶中。在真空下經由減壓蒸餾轉移(bulb-to-bulb transfer)蒸氣使所有揮發物自室溫下之反應混合物轉移至-196℃之大Schlenk燒瓶中。以乙醚中之無色溶液之形式獲得N,N'
-二甲基甲脒。1
H NMR(苯-d 6
+少量CD3
OD,ppm):7.29(s,1,CH
),2.65(br,6,NCH 3
)。
實例19.N,N' -二甲基甲脒之合成
將甲胺之鉀鹽加熱至約100℃直至其分解以得到與實例18相同之產物N,N'
-二甲基甲脒。
實例20. 四(N,N' -二甲基甲脒根基)鉿(IV)之合成
將1.16 g(3.29 mmol)四(二甲基醯胺基)鉿(IV)(即Hf(NMe2
)4
)溶於20 mL乙醚中且隨後冷卻至-30℃歷時30分鐘。向此溶液中添加0.968 g(13.4 mmol)於20 mL乙醚中之N,N'
-二甲基甲脒且在室溫下將混合物攪拌隔夜。少量白色副產物沈澱(可能是由於二甲基甲脒中之單甲基甲脒雜質)。傾析澄清上清液乙醚溶液且減壓蒸發以得到呈白色晶體之產物。其熔點為140-142℃。1
H NMR(苯-d 6
,ppm):3.03(s,24,NCH 3
),8.00(s,4,CH
)。13
C NMR(苯-d 6
,ppm):171.60(C
H),38.67(NC
H3
)。其T1/2
值為187℃且蒸發後留下可忽略之殘餘物。
圖4中比較4種不同鉿脒鹽(來自實例6、8、10及19)之蒸發速率之等溫熱解重量分析。此等量測展示在各溫度下,四(N,N'
-二甲基甲脒根基)鉿(IV)(實例20)具有最高蒸發速率。在142℃(其熔點)以上之鼓泡器溫度下,其為液體以致其高蒸發速率是極可重現的。因此,在許多應用中,四(N,N'
-二甲基甲脒根基)鉿(IV)為用於氣相沈積含鉿材料之較佳前驅體。在室溫下需要液體之應用中,其可以於具有相似沸點之溶劑中之液體溶液之形式來提供。適合溶劑包括聚醚,諸如三乙二醇二甲醚或四乙二醇二甲醚。或者,可使用室溫液態之四(N,N'
-二甲基丁脒根基)鉿(IV)以便純液體傳遞至汽化系統。
實例21. 四(N,N' -二甲基甲脒根基)鋯(IV)之合成
用四(二甲基醯胺基)鋯(IV)(即Zr(NMe2
)4
)替代四(二甲基醯胺基)鉿(IV)(即Hf(NMe2
)4
)重複實例20之步驟。獲得具有類似於四(N,N'
-二甲基甲脒根基)鉿(IV)之性質的四(N,N'
-二甲基甲脒根基)鋯(IV)。
雖然本發明已以較佳實施例揭露如上,然其並非用以限定本發明,任何熟習此技藝者,在不脫離本發明之精神和範圍內,當可作些許之更動與潤飾,因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。
11...容器
12...容器
21...四脒鹽前驅體
22...第二試劑
31...四價脒鹽前驅體之蒸氣
32...第二試劑之蒸氣
41...烘箱
42...烘箱
51...閥門
52...閥門
61...真空室
62...蒸氣空間
71...閥門
72...閥門
81...烘箱
82...烘箱
91...載氣來源
92...載氣來源
110...沈積室
120...加熱爐
130...基板
150...管道
圖1為可用於本發明之一些實施例之ALD設備的示意性橫截面圖。
圖2為四(N,N'
-二-異丁基乙脒根基)鋯(IV)之分子結構圖。
圖3為四(N,N'
-二甲基丙脒根基)鉿(IV)之分子結構圖。
圖4為4種鉿脒鹽之蒸發速率之曲線圖。
Claims (27)
- 一種化合物,具有以下結構式
- 如申請專利範圍第1項所述之化合物,其中所述金屬M是選自由鋯、鉿、錫、鉭、鈮、鎢、鉬、鈾、錸、鉑、鋨、銥、釕、鈀、鈦、銠、釩、鈰以及鉛組成之群。
- 如申請專利範圍第1項所述之化合物,其中所述金屬M是選自由鉿、鋯、鉭、鈮、鎢、鉬、錫、碲以及鈾組成之群。
- 如申請專利範圍第1項所述之化合物,其中所述金屬M為鋯。
- 如申請專利範圍第1項所述之化合物,其中所述金 屬M為鉿。
- 如申請專利範圍第1項所述之化合物,其中R1 至R12 中之至少一者為具有5個或更少碳之低級烷基。
- 如申請專利範圍第1項所述之化合物,其中R1 至R12 是選自由具有5個或更少碳之低級烷基以及氫組成之群。
- 如申請專利範圍第1項所述之化合物,其中R1 、R3 、R4 、R6 、R7 、R9 、R10 及R12 為在α-位置處無分枝之烷基。
- 一種形成包含金屬之薄膜之方法,包含:使受熱表面暴露於一或多種揮發性金屬四脒鹽化合物之蒸氣,其中所述金屬四脒鹽化合物具有以下結構式
- 如申請專利範圍第9項所述之形成包含金屬之薄膜之方法,其中所述金屬M是選自由鋯、鉿、錫、鉭、鈮、鎢、鉬、鈾、錸、鉑、鋨、銥、釕、鈀、鈦、銠、釩、鈰、碲以及鉛組成之群。
- 如申請專利範圍第9項所述之形成包含金屬之薄膜之方法,其中所述金屬M是選自由鉿、鋯、鉭、鈮、鎢、鉬、錫、碲以及鈾組成之群。
- 如申請專利範圍第9項所述之形成包含金屬之薄膜之方法,其中所述金屬M為鋯。
- 如申請專利範圍第9項所述之形成包含金屬之薄膜之方法,其中所述金屬M為鉿。
- 如申請專利範圍第9項所述之形成包含金屬之薄膜之方法,其中R1 至R12 中之至少一者為具有5個或更少碳之低級烷基。
- 如申請專利範圍第9項所述之形成包含金屬之薄膜之方法,其中R1 至R12 是選自由具有5個或更少碳之低級烷基以及氫組成之群。
- 如申請專利範圍第9項所述之形成包含金屬之薄膜之方法,其中亦將所述受熱表面暴露於氧來源,且所述薄膜包含金屬氧化物。
- 如申請專利範圍第16項所述之形成包含金屬之薄膜之方法,其中所述氧來源包含水蒸汽。
- 如申請專利範圍第16項所述之形成包含金屬之薄膜之方法,其中所述氧來源包含分子氧。
- 如申請專利範圍第16項所述之形成包含金屬之薄膜之方法,其中所述氧來源包含臭氧。
- 如申請專利範圍第9項所述之形成包含金屬之薄膜之方法,其中亦將所述受熱表面暴露於氮來源,且所述薄膜包含金屬氮化物。
- 如申請專利範圍第20項所述之形成包含金屬之薄膜之方法,其中所述氮來源包含氨。
- 如申請專利範圍第9項所述之形成包含金屬之薄膜之方法,其中所述薄膜是以化學氣相沈積方法沈積。
- 如申請專利範圍第9項所述之形成包含金屬之薄膜之方法,其中所述薄膜是以原子層沈積方法沈積。
- 如申請專利範圍第9項所述之形成包含金屬之薄膜之方法,其中所述蒸氣是藉由汽化固體金屬四脒鹽化合物而獲得。
- 如申請專利範圍第9項所述之形成包含金屬之薄膜之方法,其中所述蒸氣是藉由汽化液體金屬四脒鹽化合物而獲得。
- 如申請專利範圍第9項所述之形成包含金屬之薄膜之方法,其中所述蒸氣是藉由在100℃至250℃之範圍內之溫度下汽化金屬四脒鹽獲得。
- 如申請專利範圍第9項所述之形成包含金屬之薄膜之方法,其中所述受熱表面是處於200℃至500℃之範圍內之溫度下。
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