TWI609983B - 含鉬之薄膜之製造方法、薄膜形成用原料及鉬醯亞胺化合物 - Google Patents
含鉬之薄膜之製造方法、薄膜形成用原料及鉬醯亞胺化合物 Download PDFInfo
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- TWI609983B TWI609983B TW102138949A TW102138949A TWI609983B TW I609983 B TWI609983 B TW I609983B TW 102138949 A TW102138949 A TW 102138949A TW 102138949 A TW102138949 A TW 102138949A TW I609983 B TWI609983 B TW I609983B
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- molybdenum
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- -1 molybdenum quinone imine Chemical class 0.000 title claims description 69
- 229910052750 molybdenum Inorganic materials 0.000 title claims description 66
- 239000011733 molybdenum Substances 0.000 title claims description 66
- 239000002994 raw material Substances 0.000 title claims description 46
- 238000004519 manufacturing process Methods 0.000 title claims description 37
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims description 33
- 230000015572 biosynthetic process Effects 0.000 title description 16
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 24
- 125000000217 alkyl group Chemical group 0.000 claims description 20
- 239000000758 substrate Substances 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 14
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 13
- 230000008016 vaporization Effects 0.000 claims description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 239000010408 film Substances 0.000 description 76
- 238000000034 method Methods 0.000 description 55
- 150000001875 compounds Chemical class 0.000 description 40
- 239000007789 gas Substances 0.000 description 32
- 239000000126 substance Substances 0.000 description 28
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 24
- 239000002243 precursor Substances 0.000 description 23
- 238000000151 deposition Methods 0.000 description 21
- 230000008021 deposition Effects 0.000 description 19
- 239000000243 solution Substances 0.000 description 19
- 229910052751 metal Inorganic materials 0.000 description 16
- 239000002184 metal Substances 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 238000005229 chemical vapour deposition Methods 0.000 description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- 238000004458 analytical method Methods 0.000 description 14
- 238000004821 distillation Methods 0.000 description 14
- 230000008018 melting Effects 0.000 description 13
- 238000002844 melting Methods 0.000 description 13
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 12
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 12
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 11
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 238000001947 vapour-phase growth Methods 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 229910052787 antimony Inorganic materials 0.000 description 8
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 8
- 239000003960 organic solvent Substances 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 238000000231 atomic layer deposition Methods 0.000 description 7
- 239000002131 composite material Substances 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000012535 impurity Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- OUFGXIPMNQFUES-UHFFFAOYSA-N molybdenum ruthenium Chemical compound [Mo].[Ru] OUFGXIPMNQFUES-UHFFFAOYSA-N 0.000 description 7
- 230000001590 oxidative effect Effects 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 239000005078 molybdenum compound Substances 0.000 description 6
- 150000002752 molybdenum compounds Chemical class 0.000 description 6
- 238000005979 thermal decomposition reaction Methods 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 239000012300 argon atmosphere Substances 0.000 description 5
- 238000000921 elemental analysis Methods 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 5
- 239000013110 organic ligand Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- SWGJCIMEBVHMTA-UHFFFAOYSA-K trisodium;6-oxido-4-sulfo-5-[(4-sulfonatonaphthalen-1-yl)diazenyl]naphthalene-2-sulfonate Chemical compound [Na+].[Na+].[Na+].C1=CC=C2C(N=NC3=C4C(=CC(=CC4=CC=C3O)S([O-])(=O)=O)S([O-])(=O)=O)=CC=C(S([O-])(=O)=O)C2=C1 SWGJCIMEBVHMTA-UHFFFAOYSA-K 0.000 description 5
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 229910052797 bismuth Inorganic materials 0.000 description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 4
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 4
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 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 4
- 239000002245 particle Substances 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- 238000009834 vaporization Methods 0.000 description 4
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 3
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000006837 decompression Effects 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 238000002309 gasification Methods 0.000 description 3
- GRMPXSPEDGUDDD-UHFFFAOYSA-N molybdenum dihydride Chemical compound [MoH2] GRMPXSPEDGUDDD-UHFFFAOYSA-N 0.000 description 3
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 150000004060 quinone imines Chemical class 0.000 description 3
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 3
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000013022 venting Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QEGNUYASOUJEHD-UHFFFAOYSA-N 1,1-dimethylcyclohexane Chemical compound CC1(C)CCCCC1 QEGNUYASOUJEHD-UHFFFAOYSA-N 0.000 description 2
- NWFVDKHZNWEXAD-UHFFFAOYSA-N 1-tert-butylcyclopenta-1,3-diene Chemical compound CC(C)(C)C1=CC=CC1 NWFVDKHZNWEXAD-UHFFFAOYSA-N 0.000 description 2
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 2
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 description 2
- HCFAJYNVAYBARA-UHFFFAOYSA-N 4-heptanone Chemical compound CCCC(=O)CCC HCFAJYNVAYBARA-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000005909 Kieselgur Substances 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- PIBIXIANRYAGAU-UHFFFAOYSA-N [Mo].O1CCCC1 Chemical compound [Mo].O1CCCC1 PIBIXIANRYAGAU-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 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 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 125000005594 diketone group Chemical group 0.000 description 2
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 2
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- TXGJTWACJNYNOJ-UHFFFAOYSA-N hexane-2,4-diol Chemical compound CCC(O)CC(C)O TXGJTWACJNYNOJ-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 239000012434 nucleophilic reagent Substances 0.000 description 2
- 238000006864 oxidative decomposition reaction Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- TVSBRLGQVHJIKT-UHFFFAOYSA-N propan-2-ylcyclopentane Chemical compound CC(C)C1CCCC1 TVSBRLGQVHJIKT-UHFFFAOYSA-N 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 150000003304 ruthenium compounds Chemical class 0.000 description 2
- AXTNEYPUUFCBII-UHFFFAOYSA-N sodium;5-methylcyclopenta-1,3-diene Chemical compound [Na+].C[C-]1C=CC=C1 AXTNEYPUUFCBII-UHFFFAOYSA-N 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 2
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- BVPKYBMUQDZTJH-UHFFFAOYSA-N 1,1,1-trifluoro-5,5-dimethylhexane-2,4-dione Chemical compound CC(C)(C)C(=O)CC(=O)C(F)(F)F BVPKYBMUQDZTJH-UHFFFAOYSA-N 0.000 description 1
- VNPQQEYMXYCAEZ-UHFFFAOYSA-N 1,2,3,4-tetramethylcyclopenta-1,3-diene Chemical compound CC1=C(C)C(C)=C(C)C1 VNPQQEYMXYCAEZ-UHFFFAOYSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- SIUWDFVMEASCRP-UHFFFAOYSA-N 1-(2-methoxyethoxy)-2-methylpropan-2-ol Chemical compound COCCOCC(C)(C)O SIUWDFVMEASCRP-UHFFFAOYSA-N 0.000 description 1
- GHJATKVLNMETBA-UHFFFAOYSA-N 1-(2-methylpropyl)cyclopenta-1,3-diene Chemical compound CC(C)CC1=CC=CC1 GHJATKVLNMETBA-UHFFFAOYSA-N 0.000 description 1
- JCALRHVFTLBTOZ-UHFFFAOYSA-N 1-butoxy-2-methylpropan-2-ol Chemical compound CCCCOCC(C)(C)O JCALRHVFTLBTOZ-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- FTFYDDRPCCMKBT-UHFFFAOYSA-N 1-butylcyclopenta-1,3-diene Chemical compound CCCCC1=CC=CC1 FTFYDDRPCCMKBT-UHFFFAOYSA-N 0.000 description 1
- BCYNAHGOLUTMDM-UHFFFAOYSA-N 1-ethoxy-2-methylpropan-2-ol Chemical compound CCOCC(C)(C)O BCYNAHGOLUTMDM-UHFFFAOYSA-N 0.000 description 1
- IQSUNBLELDRPEY-UHFFFAOYSA-N 1-ethylcyclopenta-1,3-diene Chemical compound CCC1=CC=CC1 IQSUNBLELDRPEY-UHFFFAOYSA-N 0.000 description 1
- QNLXXWOBNIYLGO-UHFFFAOYSA-N 1-methoxy-2,2,6,6-tetramethylheptane-3,5-dione Chemical compound COCC(C)(C)C(=O)CC(=O)C(C)(C)C QNLXXWOBNIYLGO-UHFFFAOYSA-N 0.000 description 1
- MXUXZWFVAPTPAG-UHFFFAOYSA-N 1-methoxy-2-methylpropan-2-ol Chemical compound COCC(C)(C)O MXUXZWFVAPTPAG-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- RZPAXISDLOEXPI-UHFFFAOYSA-N 1-propylcyclopenta-1,3-diene Chemical compound CCCC1=CC=CC1 RZPAXISDLOEXPI-UHFFFAOYSA-N 0.000 description 1
- YRAJNWYBUCUFBD-UHFFFAOYSA-N 2,2,6,6-tetramethylheptane-3,5-dione Chemical compound CC(C)(C)C(=O)CC(=O)C(C)(C)C YRAJNWYBUCUFBD-UHFFFAOYSA-N 0.000 description 1
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- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F17/00—Metallocenes
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- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic Table
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
- C23C16/18—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metallo-organic compounds
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- 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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- 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
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
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- Mechanical Engineering (AREA)
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- Inorganic Chemistry (AREA)
- Chemical Vapour Deposition (AREA)
- Formation Of Insulating Films (AREA)
- Electroluminescent Light Sources (AREA)
Description
本發明係關於一種使用使特定之鉬醯亞胺化合物氣化而獲得之蒸氣的含有鉬之薄膜之製造方法、藉由該製造方法所製造之含有鉬之薄膜、用於該製造方法之薄膜形成用原料及新穎之鉬醯亞胺化合物。
含有鉬之薄膜可用於有機發光二極體、液晶顯示器、電漿顯示面板、場發射顯示器、薄膜太陽電池、低電阻歐姆電極以及其他電子器件及半導體器件，主要用作障壁膜等電子零件之構件。
作為上述薄膜之製造法，可列舉濺鍍法、離子鍍著法、塗佈熱分解法或溶膠凝膠法等MOD(Metal Organic Deposition，金屬有機沈積)法、化學氣相成長法等，由於具有組成控制性及階差被覆性優異、適合量產化、可進行混合積體等眾多優點，包含ALD(Atomic Layer Deposition，原子層沈積)法之化學氣相成長(以下，有時亦僅記載為CVD)法為最適合之製造製程。
用作CVD法用原料之鉬化合物先前已知有各種鉬化合物。例如，專利文獻1中報告有雙環戊二烯基鉬二氫化物、雙甲基環戊二烯基鉬二氫化物、雙乙基環戊二烯基鉬二氫化物、及雙異丙基環戊二烯基鉬二氫化物。然而，專利文獻1中揭示之化合物有熔點較高，蒸氣壓較低，由加熱引起之熱分解後產生大量殘渣之問題，並非作為CVD法用原料可令人充分滿意之化合物。
又，非專利文獻1中報告有雙環戊二烯基醯亞胺鉬化合物。然
而，非專利文獻1中並未就雙環戊二烯基醯亞胺鉬化合物可用作CVD法用原料進行揭示。
專利文獻1：US20060068100A1
非專利文獻
非專利文獻1：J. CHEM. SOC. DALTON TRANS 1995 P. 155-162
於利用CVD法之含有鉬之薄膜之製造中，迄今為止提出之鉬化合物未必可謂具有充分之特性。適合於CVD法等之使化合物氣化而形成薄膜之原料的化合物(前驅物)所要求之性質為熱穩定性較高、熔點較低、蒸氣壓較大容易氣化。先前之用作鉬源之化合物有熔點較高、蒸氣壓較低、及由加熱引起之熱分解後產生大量殘渣之問題。若由加熱引起之熱分解物之殘分大量產生，則該殘分成為導致微粒之原因，從而有所期望之薄膜之膜質劣化、配管或容器之洗淨變得困難、配管堵塞之問題發生之情形。
本發明者等進行反覆研究，結果發現，將特定之鉬醯亞胺化合物用作前驅物的利用CVD法之含有鉬之薄膜之製造方法可解決上述課題，從而達成本發明。
本發明提供一種薄膜之製造方法、藉由上述薄膜製造方法所製造之含有鉬之薄膜，上述薄膜之製造方法係將使含有下述通式(I)所表示之鉬醯亞胺化合物而成之薄膜形成用原料氣化而獲得的含有鉬醯亞胺化合物之蒸氣導入至基體上，使其分解及/或進行化學反應，而於基體上形成含有鉬之薄膜。
(式中，R1~R10表示氫原子或碳數1~5之直鏈或支鏈狀烷基，R11表示碳數1~8之直鏈或支鏈狀烷基)
又，本發明提供一種含有上述通式(I)所表示之鉬醯亞胺化合物而成之薄膜形成用原料。
又，本發明提供一種下述通式(II)所表示之新穎之鉬醯亞胺化合物。
(式中，R12~R21表示氫原子或碳數1~5之直鏈或支鏈狀烷基，R22、R23分別表示甲基或乙基，R24表示碳數2~5之直鏈或支鏈狀烷基)
根據本發明，藉由使用含有特定之鉬醯亞胺化合物而成之薄膜
形成用原料，由於該化合物為熱穩定性優異、熔點較低、蒸氣壓較高之化合物，故而於利用CVD法之含有鉬之薄膜之製造中，前驅物之輸送性優異、容易控制向基體之供給量且可穩定地供給，從而可量產性良好地製造優質之含有鉬之薄膜。
圖1係表示本發明之含有鉬之薄膜之製造方法中所使用的化學氣相成長用裝置之一例之概要圖。
圖2係表示本發明之含有鉬之薄膜之製造方法中所使用的化學氣相成長用裝置之另一例之概要圖。
圖3係表示本發明之含有鉬之薄膜之製造方法中所使用的化學氣相成長用裝置之另一例之概要圖。
圖4係表示本發明之含有鉬之薄膜之製造方法中所使用的化學氣相成長用裝置之另一例之概要圖。
以下，對本發明之含有鉬之薄膜之製造方法之較佳實施形態進行詳細說明。
本發明之上述通式(I)中，作為R1~R10所表示之碳數1~5之直鏈或支鏈狀烷基，例如可列舉：甲基、乙基、丙基、異丙基、丁基、第二丁基、第三丁基、異丁基、戊基、第二戊基、第三戊基、異戊基、新戊基，作為R11所表示之碳數1~8之直鏈或支鏈狀烷基，例如可列舉：甲基、乙基、丙基、異丙基、丁基、第二丁基、第三丁基、異丁基、戊基、第二戊基、第三戊基、異戊基、新戊基、己基、2-己基、3-己基、環己基、1-甲基環己基、庚基、2-庚基、3-庚基、異庚基、第三庚基、正辛基、異辛基、第三辛基、2-乙基己基等。
作為具有此種基之鉬醯亞胺化合物之具體例，例如可列舉下述所示之化合物No.1~63。但，本發明不受以下例示化合物任何限定。
本發明之含有鉬之薄膜之製造方法所使用之鉬醯亞胺化合物中，上述通式(I)之R1~R10較佳為使化合物之熔點較低、蒸氣壓較大者，具體而言，R1~R10較佳為氫原子或甲基，R1~R10全部為氫原子者，或R1~R5中一個為甲基、進而R6~R10中一個為甲基者由於蒸氣壓較大，故而尤佳。R11若為三級烷基，則熔點較低，故而較佳，其中較佳為第三丁基、第三戊基或1,1,3,3-四甲基丁基。R11為第三戊基或1,1,3,3-四甲基丁基者特別是熔點較低，故而尤佳。
所謂本發明之薄膜形成用原料，係將上述說明之鉬醯亞胺化合
物設為含有鉬之薄膜製造用之前驅物者，其根據製程而形態各異。通式(I)所表示之鉬醯亞胺化合物根據其物性，作為化學氣相成長法用原料而特別有用。
於本發明之薄膜形成用原料為化學氣相成長法用原料之情形時，其形態係根據所使用之化學氣相成長法之輸送供給方法等方法而適當選擇者。
作為上述輸送供給方法，有以下方法：氣體輸送法，藉由將化學氣相成長用原料於原料容器中進行加熱及/或減壓使其氣化，並與視需要使用之氬氣、氮氣、氦氣等載氣一起導入至沈積反應部；液體輸送法，將化學氣相成長用原料以液體或溶液之狀態輸送至氣化室，於氣化室進行加熱及/或減壓，藉此使其氣化並導入至沈積反應部。於氣體輸送法之情形時，上述通式(I)所表示之鉬醯亞胺化合物其本身成為化學氣相成長用原料，於液體輸送法之情形時，上述通式(I)所表示之鉬醯亞胺化合物其本身或將該化合物溶解於有機溶劑所成之溶液成為化學氣相成長用原料。
又，於多成分系之化學氣相成長法中，有將化學氣相成長用原料各成分獨立地進行氣化、供給之方法(以下，有時亦記載為單源法)、與將預先以所期望之組成混合多成分原料所成之混合原料進行氣化、供給之方法(以下，有時亦記載為混合源法)。於混合源法之情形時，上述通式(I)所表示之鉬醯亞胺化合物與其他前驅物之混合物或混合溶液為化學氣相成長用原料。
作為上述化學氣相成長用原料所使用之有機溶劑，不受特別限制，可使用周知一般之有機溶劑。作為該有機溶劑，例如可列舉：乙酸乙酯、乙酸丁酯、乙酸甲氧基乙酯等乙酸酯類；乙二醇單甲醚、乙二醇單乙醚、乙二醇單丁醚、二乙二醇單甲醚等醚醇類；四氫呋喃、四氫吡喃、乙二醇二甲醚、二乙二醇二甲醚、三乙二醇二甲醚、二丁
醚、二
烷等醚類；甲基丁基酮、甲基異丁基酮、乙基丁基酮、二丙基酮、二異丁基酮、甲基戊基酮、環己酮、甲基環己酮等酮類；己烷、環己烷、甲基環己烷、二甲基環己烷、乙基環己烷、庚烷、辛烷、甲苯、二甲苯等烴類；1-氰基丙烷、1-氰基丁烷、1-氰基己烷、氰基環己烷、氰基苯、1,3-二氰基丙烷、1,4-二氰基丁烷、1,6-二氰基己烷、1,4-二氰基環己烷、1,4-二氰基苯等具有氰基之烴類；吡啶、二甲基吡啶；該等根據溶質之溶解性、使用溫度與沸點、燃點(firing point)之關係等，可單獨或作為二種以上混合溶劑使用。於使用該等有機溶劑之情形時，較佳為使該有機溶劑中之上述通式(I)所表示之鉬醯亞胺化合物及其他前驅物之合計量成為0.01~2.0莫耳/升、尤其是0.05~1.0莫耳/升。
又，於多成分系之化學氣相成長用原料之情形時，作為與上述鉬醯亞胺化合物一起使用之其他前驅物，不受特別限制，可使用化學氣相成長用原料所使用之周知一般之前驅物。
作為上述其他前驅物，可列舉選自醇化合物、二醇化合物、β-二酮化合物、環戊二烯化合物及有機胺化合物等中之一種或二種以上之有機配位化合物與矽或金屬之化合物。又，作為前驅物之金屬種，可列舉：鋰、鈉、鉀、鎂、鈣、鍶、鋇、鈦、鋯、鉿、釩、鈮、鉭、鉬、錳、鐵、釕、鈷、銠、銥、鎳、鈀、鉑、銅、銀、金、鋅、鋁、鎵、銦、鍺、錫、鉛、銻、鉍、釔、鑭、鈰、鐠、釹、鉕、釤、銪、釓、鋱、鏑、鈥、鉺、銩、鐿。
作為上述用作有機配位子之醇化合物，可列舉：甲醇、乙醇、丙醇、異丙醇、丁醇、2-丁醇、異丁醇、第三丁醇、戊醇、異戊醇、第三戊醇等烷基醇類；2-甲氧基乙醇、2-乙氧基乙醇、2-丁氧基乙醇、2-(2-甲氧基乙氧基)乙醇、2-甲氧基-1-甲基乙醇、2-甲氧基-1,1-二甲基乙醇、2-乙氧基-1,1-二甲基乙醇、2-異丙氧基-1,1-二甲基乙
醇、2-丁氧基-1,1-二甲基乙醇、2-(2-甲氧基乙氧基)-1,1-二甲基乙醇、2-丙氧基-1,1-二乙基乙醇、2-第二丁氧基-1,1-二乙基乙醇、3-甲氧基-1,1-二甲基丙醇等醚醇類。
作為上述用作有機配位子之二醇化合物，可列舉：1,2-乙二醇、1,2-丙二醇、1,3-丙二醇、2,4-己二醇、2,2-二甲基-1,3-丙二醇、2,2-二乙基-1,3-丙二醇、1,3-丁二醇、2,4-丁二醇、2,2-二乙基-1,3-丁二醇、2-乙基-2-丁基-1,3-丙二醇、2,4-戊二醇、2-甲基-1,3-丙二醇、2-甲基-2,4-戊二醇、2,4-己二醇、2,4-二甲基-2,4-戊二醇。
作為上述用作有機配位子之β-二酮化合物，可列舉：乙醯丙酮、己烷-2,4-二酮、5-甲基己烷-2,4-二酮、庚烷-2,4-二酮、2-甲基庚烷-3,5-二酮、5-甲基庚烷-2,4-二酮、6-甲基庚烷-2,4-二酮、2,2-二甲基庚烷-3,5-二酮、2,6-二甲基庚烷-3,5-二酮、2,2,6-三甲基庚烷-3,5-二酮、2,2,6,6-四甲基庚烷-3,5-二酮、辛烷-2,4-二酮、2,2,6-三甲基辛烷-3,5-二酮、2,6-二甲基辛烷-3,5-二酮、2,9-二甲基壬烷-4,6-二酮、2-甲基-6-乙基癸烷-3,5-二酮、2,2-二甲基-6-乙基癸烷-3,5-二酮等烷基取代β-二酮類；1,1,1-三氟戊烷-2,4-二酮、1,1,1-三氟-5,5-二甲基己烷-2,4-二酮、1,1,1,5,5,5-六氟戊烷-2,4-二酮、1,3-二全氟己基丙烷-1,3-二酮等氟取代烷基β-二酮類；1,1,5,5-四甲基-1-甲氧基己烷-2,4-二酮、2,2,6,6-四甲基-1-甲氧基庚烷-3,5-二酮、2,2,6,6-四甲基-1-(2-甲氧基乙氧基)庚烷-3,5-二酮等醚取代β-二酮類。
作為上述用作有機配位子之環戊二烯化合物，可列舉：環戊二烯、甲基環戊二烯、乙基環戊二烯、丙基環戊二烯、異丙基環戊二烯、丁基環戊二烯、第二丁基環戊二烯、異丁基環戊二烯、第三丁基環戊二烯、二甲基環戊二烯、四甲基環戊二烯等，作為用作有機配位子之有機胺化合物，可列舉：甲基胺、乙基胺、丙基胺、異丙基胺、丁基胺、第二丁基胺、第三丁基胺、異丁基胺、二甲基胺、二乙基
胺、二丙基胺、二異丙基胺、乙基甲基胺、丙基甲基胺、異丙基甲基胺等。
於單源法之情形時，上述其他前驅物較佳為熱及/或氧化分解之行為類似之化合物，於混合源法之情形時，上述其他前驅物較佳為除了熱及/或氧化分解之行為類似以外，於混合時亦不發生由化學反應引起之變質者。
對於本發明之化學氣相成長用原料，使其儘量不含有構成其之成分以外之雜質金屬元素成分、雜質氯等雜質鹵素成分、及雜質有機成分。雜質金屬元素成分較佳為每種元素為100ppb以下，更佳為10ppb以下，以總量計較佳為1ppm以下，更佳為100ppb以下。尤其是於用作LSI之閘極絕緣膜、閘極膜、障壁層之情形時，必須減少對所得之電薄膜之電氣特性有影響之鹼金屬元素、鹼土金屬元素、及同屬元素(鉻或鎢)之含量。雜質鹵素成分較佳為100ppm以下，更佳為10ppm以下，進而較佳為1ppm以下。雜質有機成分以總量計較佳為500ppm以下，更佳為50ppm以下，進而較佳為10ppm以下。又，水分成為化學氣相成長用原料中之微粒發生、或薄膜形成中之微粒發生之原因，故而對於金屬化合物、有機溶劑、及親核性試劑，較佳為於使用時預先儘可能地去除水分以減少各自之水分。金屬化合物、有機溶劑及親核性試劑各自之水分量較佳為10ppm以下，進而較佳為1ppm以下。
又，對於本發明之化學氣相成長用原料，為降低或防止所形成之薄膜之微粒污染，較佳為使其儘量不含有微粒。具體而言，於在液相中利用光散射式液中粒子檢測器之微粒測定中，較佳為大於0.3μm之粒子之個數於液相1ml中為100個以下，更佳為大於0.2μm之粒子之個數於液相1ml中為1000個以下，進而較佳為大於0.2μm之粒子之個數於液相1ml中為100個以下。
本發明之含有鉬之薄膜之製造方法係利用以下化學氣相成長用法者，即，將使上述通式(I)所表示之鉬醯亞胺化合物氣化而獲得的含有鉬醯亞胺化合物之氣體、及視需要使用之使其他前驅物氣化所成之氣體與反應性氣體導入至基體上，繼而，使鉬醯亞胺化合物、及視需要使用之其他前驅物於基體上分解及/或反應，而於基體上成長、沈積所期望之薄膜。關於原料之輸送供給方法、沈積方法、製造條件、製造裝置等並不受特別限制，可使用周知一般之條件、方法。
作為上述視需要使用之反應性氣體，例如作為氧化性者，可列舉：氧氣、臭氧、二氧化氮、一氧化氮、水蒸氣、過氧化氫、甲酸、乙酸、乙酸酐等，作為還原性者，可列舉氫，又，作為製造氮化物者，可列舉：單烷基胺、二烷基胺、三烷基胺、伸烷基二胺等有機胺化合物、肼、氨等，該等可使用1種或2種以上。
又，作為上述輸送供給方法，可列舉上述記載之氣體輸送法、液體輸送法、單源法、混合源法等。
又，作為上述沈積方法，可列舉：使鉬醯亞胺化合物(及其他前驅物氣體)與反應性氣體僅藉由熱進行反應而沈積薄膜之熱CVD法；使用熱與電漿之電漿CVD法；使用熱與光之光CVD法；使用熱、光及電漿之光電漿CVD法；將CVD法之沈積反應分為基本過程，按分子等級階段性地進行沈積之ALD法。
作為上述基體之材質，例如可列舉：矽；氮化矽、氮化鈦、氮化鉭、氧化鈦、氮化鈦、氧化釕、氧化鋯、氧化鉿、氧化鑭等陶瓷；玻璃；金屬釕等金屬。作為基體之形狀，可列舉板狀、球狀、纖維狀、鱗片狀，基體表面可為平面，亦可成為溝渠結構等三維結構。
又，作為上述製造條件，可列舉反應溫度(基體溫度)、反應壓力、沈積速度等。關於反應溫度，較佳為上述鉬醯亞胺化合物充分反應之溫度即100℃以上，更佳為100~300℃。又，反應壓力於熱CVD
法、光CVD法、電漿CVD法之情形時較佳為0.01~300Pa。又，沈積速度可根據原料之供給條件(氣化溫度、氣化壓力)、反應溫度、反應壓力進行控制。若沈積速度較大，則有所得之薄膜之特性惡化之情形，若沈積速度較小，則有生產性方面產生問題之情形，故而較佳為0.2~40.0nm/min，更佳為4.0~25.0nm/min。又，於ALD法之情形時，以循環之次數進行控制以獲得所期望之膜厚。
例如，於藉由ALD法形成氧化鉬薄膜之情形時，進行以下原料導入步驟，即，藉由上述輸送供給方法使薄膜形成用原料氣化形成蒸氣，將該蒸氣導入至基體上(具體為設置有基體之沈積反應部內)。繼而，藉由導入至沈積反應部之鉬醯亞胺化合物，於基體上成膜前驅物薄膜(前驅物薄膜成膜步驟)。此時，可加熱基體或加熱沈積反應部而施加熱。該步驟中成膜之前驅物薄膜為鉬醯亞胺薄膜、或鉬醯亞胺化合物之一部分解及/或反應所生成之薄膜，其具有與目標之氧化鉬薄膜不同之組成。進行本步驟之溫度較佳為室溫~500℃，更佳為100~300℃。
繼而，自沈積反應部排出未反應之鉬醯亞胺化合物氣體或副生成之氣體(排氣步驟)。未反應之鉬醯亞胺化合物氣體或副生成之氣體自沈積反應部完全排出較為理想，但未必必須完全排出。作為排氣方法，可列舉藉由氦氣、氬氣等惰性氣體對系統內進行吹拂之方法、藉由對系統內減壓而排氣之方法、及組合有該等之方法等。進行減壓之情形之減壓度較佳為0.01~300Pa，更佳為0.1~100Pa。
繼而，向沈積反應部導入氧化性氣體，藉由該氧化性氣體、氧化性氣體及熱之作用，由之前之前驅物薄膜成膜步驟中獲得之前驅物薄膜形成氧化鉬薄膜(氧化鉬薄膜形成步驟)。本步驟中，使熱作用之情形之溫度較佳為室溫~500℃，更佳為100~300℃。通式(I)所表示之鉬醯亞胺化合物與氧化性氣體之反應性良好，可獲得氧化鉬薄膜。
亦可將藉由上述包含原料導入步驟、前驅物薄膜成膜步驟、排氣步驟、及氧化鉬薄膜形成步驟之一系列操作進行之薄膜沈積設為1次循環，重複複數次該循環直至獲得必要膜厚之薄膜。於該情形時，較佳為進行1次循環後，與上述排氣步驟同樣地自沈積反應部排出未反應之鉬醯亞胺化合物氣體及氧化性氣體、進而副生成之氣體，然後進行下1次循環。
又，於氧化鉬薄膜之藉由ALD法之形成中，亦可施加電漿、光、電壓等能量。施加該等能量之時期並無特別限定，例如可為原料導入步驟中之鉬醯亞胺化合物氣體導入時、前驅物薄膜成膜步驟或氧化鉬薄膜形成步驟中之加溫時、排氣步驟中之系統內之排氣時、氧化鉬薄膜形成步驟中之氧化性氣體導入時，亦可為上述各步驟之間。
於本發明之薄膜形成方法中，可於薄膜沈積之後，為獲得更良好之膜質，而於惰性環境下、氧化性氣體或還原性氣體環境下進行退火處理，於必需階差覆蓋性之情形，亦可設置回焊步驟。該情形之溫度較佳為400~1200℃，尤佳為500~800℃。
使用本發明之薄膜形成用原料製造薄膜之裝置可使用周知之化學氣相成長法用裝置。作為具體之裝置之例，可列舉如圖1之可起泡供給前驅物而進行製造之裝置、或如圖2般包含氣化室之裝置。又，可列舉如圖3、圖4般可對反應性氣體進行電漿處理之裝置。並不限於如圖1、圖2、圖3、圖4之單片式裝置，亦可使用利用批次爐之能同時處理多片之裝置。上述沈積反應部相當於圖1~圖4中之成膜室。
作為使用本發明之化學氣相成長用原料所形成製造之含有鉬之薄膜，例如可列舉：金屬鉬、氮化鉬、二氧化鉬、三氧化鉬、鉬-鈉系複合氧化物、鉬-鈣系複合氧化物、鉬-鉍系複合氧化物、鉬-鈮系複合氧化物、鉬-鋅系複合氧化物、鉬-矽系複合氧化物、鉬-鈰系複合氧化物等，作為該等之用途，除如電極、障壁膜之電子零件構件以外，
亦可列舉：觸媒、觸媒用原料、金屬用原料、金屬表面處理劑、陶瓷添加劑、燒結金屬添加劑、阻燃劑、滅煙劑、防凍液用原料、無機顏料用顯色劑、鹼性染料媒染劑、防銹劑原料、農業用微量肥料、窯業用副原料。
本發明之上述通式(I)所表示之鉬醯亞胺化合物不會受其製造方法特別限制，可應用周知之反應進行製造。作為製造方法，只要應用使用適合之醯亞胺化合物之周知一般之金屬醯亞胺化合物之合成方法即可。例如可列舉使對應之結構之烷基醯亞胺鹵化氧鉬化合物視需要與三苯基膦反應，進而與對應之結構之環戊二烯化合物衍生物反應之方法。
本發明之新穎鉬醯亞胺化合物為上述通式(II)所表示之化合物。本發明之新穎鉬醯亞胺化合物由於熔點較低、蒸氣壓較高，故而係特別適合作為CVD法等包含氣化步驟之薄膜製造方法之前驅物之化合物。
本發明之上述通式(II)中，R12~R21表示氫原子或碳數1~5之直鏈或支鏈狀烷基。作為該碳數1~5之直鏈或支鏈狀烷基，例如可列舉：甲基、乙基、丙基、異丙基、丁基、第二丁基、第三丁基、異丁基、戊基、第二戊基、第三戊基、異戊基、新戊基。上述通式(II)之R12~R21較佳為使化合物之熔點較低、蒸氣壓較大者，具體而言，R12~R21較佳為氫原子或甲基，R12~R21全部為氫原子者，或R12~R16中一個為甲基、進而R17~R21中一個為甲基者由於蒸氣壓較大，故而尤佳。又，本發明之上述通式(II)中，R22、R23分別表示甲基或乙基，有根據所選擇之基，R22及R23所鍵結之碳具有光學活性之情形，並未藉由R體、S體而特別區分，可為其任一者，R體與S體亦可為混合物。外消旋體之製造成本低廉。於R22、R23中至少一個為甲基之情形時，蒸氣壓較高而較佳。又，本發明之上述通式(II)中，作為R24所表示之
碳數2~5之直鏈或支鏈狀烷基，例如可列舉：乙基、丙基、異丙基、丁基、第二丁基、第三丁基、異丁基、戊基、第二戊基、第三戊基、異戊基、新戊基。本發明之上述通式(II)中，R12~R21為氫原子、R22、R23為甲基、R24為乙基或新戊基之化合物，或R12~R16中一個為甲基、R17~R21中一個為甲基、R22、R23為甲基、R24為乙基或新戊基之化合物由於熔點較低、蒸氣壓較大，故而較佳，其中，R12~R21為氫原子、R22、R23為甲基、R24為新戊基之化合物，或R12~R16中一個為甲基、R17~R21中一個為甲基、R22、R23為甲基、R24為乙基或新戊基之化合物由於熔點非常低，故而尤佳。
作為本發明之上述通式(II)所表示之化合物之具體例，例如可列舉上述化合物No.9、19、30及40等。但，本發明不受上述例示化合物任何限定。
本發明之上述通式(II)所表示之鉬醯亞胺化合物不會受其製造方法特別限制，可應用周知之反應進行製造。作為製造方法，只要應用使用適合之醯亞胺化合物之周知一般之金屬醯亞胺化合物之合成方法即可。例如可列舉使對應之結構之烷基醯亞胺鹵化氧鉬化合物視需要與三苯基膦反應，進而與對應之結構之環戊二烯化合物衍生物反應之方法。
以下，利用製造例、評價例、實施例對本發明進行更詳細之說明。然而，本發明不受以下實施例等任何限制。
於乾燥氬氣環境下，向500mL反應燒瓶中添加第三丁基醯亞胺-二氯氧鉬之四氫呋喃30.7質量%溶液81.4g(0.07莫耳)、及三苯基膦之四氫呋喃溶液26.9質量%溶液76.9g(0.08莫耳)，於室溫下反應16小時。向該鉬溶液中滴加環戊二烯基鈉之四氫呋喃溶液(0.18莫耳)後，
進行6小時回流。利用減壓蒸餾去除將溶劑濃縮，添加己烷進行3小時回流，將溫度降至室溫，藉由G4波爾濾器進行過濾。利用減壓蒸餾去除將該濾液濃縮，於120℃、40Pa下進行昇華，藉此獲得粗製物，然後將溶解於己烷之溶液冷卻至-30℃進行再結晶，藉此獲得化合物No.6。對所得之暗紫紅色固體進行以下之分析。
(1)元素分析(金屬分析：ICP-AES(Inductively Coupled Plasma-Atomic Emission Spectrometry，感應耦合電漿-原子發射光譜法))
鉬：31.97質量%(理論值32.28%)；C：56.2質量%、H：6.7質量%、N：4.9質量%(理論值係C：56.6%、H：6.4%、N：4.7%)
(2)1H-NMR(溶劑：氘苯)(化學位移：多重性：H數)
(1.04：s：9)(5.12：s：10)
(3)TG-DTA(Thermogravimetric/Differential Thermal Analysis，熱重差熱分析)
(Ar：100ml/min、升溫：10℃/min、樣品量：9.177mg)
減少50質量%時之溫度：219℃
於乾燥氬氣環境下，向500mL反應燒瓶中添加第三丁基醯亞胺-二氯氧鉬之四氫呋喃36.2質量%溶液138.83g(0.15莫耳)及三苯基膦0.03莫耳，於室溫下反應16小時。向該鉬溶液中滴加甲基環戊二烯基鈉之四氫呋喃溶液(0.32莫耳)後，進行6小時回流。利用減壓蒸餾去除將溶劑濃縮，添加己烷進行15分鐘回流，將溫度降至室溫，添加矽藻土11.5g，利用0.5μm過濾器進行過濾。利用減壓蒸餾去除將該濾液濃縮，藉由減壓蒸餾分取40Pa、塔頂溫度116~119℃之餾分，藉此獲得化合物No.27。對所得之暗紫紅色固體進行以下之分析。
(1)元素分析(金屬分析：ICP-AES)
鉬：38.8質量%(理論值29.49%)、C：58.6質量%、H：6.7質量%、N：4.5質量%(理論值係C：59.1%、H：7.1%、N：4.3%)
(2)1H-NMR(溶劑：氘苯)(化學位移：多重性：H數)
(1.10：s：9)(1.91：s：6)(4.82：t：4)(5.23：t：4)
(3)TG-DTA
(Ar：100ml/min、升溫：10℃/min、樣品量：10.314mg)
減少50質量%時之溫度：222℃
於乾燥氬氣環境下，向500mL反應燒瓶中添加1,1,3,3-四甲基丁基醯亞胺-二氯氧鉬之四氫呋喃38.0質量%溶液158.1g(0.15莫耳)及三苯基膦0.03莫耳，於室溫下反應20小時。向該鉬溶液中滴加環戊二烯基鈉之四氫呋喃溶液(0.32莫耳)後，進行6小時回流。利用減壓蒸餾去除將溶劑濃縮，添加己烷及矽藻土，藉由0.5μm過濾器進行過濾。利用減壓蒸餾去除將該濾液濃縮，藉由減壓蒸餾分取45Pa、塔頂溫度136℃之餾分，藉此獲得化合物No.19。對所得之暗紫紅色液體進行以下之分析。
(1)元素分析(金屬分析：ICP-AES)
鉬：26.1質量%(理論值27.15%)、C：60.7質量%、H：7.2質量%、N：3.8質量%(理論值係C：61.2%、H：7.7%、N：4.0%)
(2)1H-NMR(溶劑：氘苯)(化學位移：多重性：H數)
(1.02：s：9)(1.10：s：6)(1.39：s：2)(5.12：s：10)
(3)TG-DTA
(Ar：100ml/min、升溫：10℃/min、樣品量：10.411mg)
減少50質量%時之溫度：251℃
於乾燥氬氣環境下，向500mL反應燒瓶中滴加第三戊基醯亞胺-二氯氧鉬之四氫呋喃39.6質量%溶液75.76g(0.08莫耳)及甲基環戊二烯基鈉之四氫呋喃溶液(0.18莫耳)後，進行6小時回流。利用減壓蒸餾去除將溶劑濃縮，添加己烷進行2小時回流，將溫度降至室溫，利用0.5μm過濾器進行過濾。利用減壓蒸餾去除將該濾液濃縮，藉由減壓蒸餾分取40Pa、塔頂溫度118~121℃之餾分，藉此獲得化合物No.30。對所得之暗紫紅色液體進行以下之分析。
(1)元素分析(金屬分析：ICP-AES)
鉬：28.7質量%(理論值28.27%)、C：60.7質量%、H：7.2質量%、N：4.3質量%(理論值係C：60.2%、H：7.4%、N：4.1%)
(2)1H-NMR(溶劑：氘苯)(化學位移：多重性：H數)
(0.93：t：3)(1.03：s：6)(1.32：q：2)(1.92：s：6)(4.76：t：4)(5.25：t：4)
(3)TG-DTA
(Ar：100ml/min、升溫：10℃/min、樣品量：10.932mg)
減少50質量%時之溫度：236℃
於乾燥氬氣環境下，向500mL反應燒瓶中添加1,1,3,3-四甲基丁基醯亞胺-二氯氧鉬0.062莫耳、四氫呋喃0.625莫耳及三苯基膦0.01莫耳，於室溫下反應20小時。向該鉬溶液中滴加甲基環戊二烯基鈉之四氫呋喃溶液(0.131莫耳)後，進行6小時回流。利用減壓蒸餾去除將溶劑濃縮，添加己烷及矽藻土，利用0.5μm過濾器進行過濾。利用減壓蒸餾去除將該濾液濃縮，藉由減壓蒸餾分取33Pa、塔頂溫度142℃之餾分，藉此獲得化合物No.40。對所得之暗紫紅色液體進行以下之分
析。
(1)元素分析(金屬分析：ICP-AES)
鉬：24.7質量%(理論值25.154%)、C：62.5質量%、H：8.4質量%、N：3.8質量%(理論值係C：63.0%、H：8.2%、N：3.7%)
(2)1H-NMR(溶劑：氘苯)(化學位移：多重性：H數)
(1.03：s：9)(1.15：s：6)(1.46：s：2)(1.93：s：6)(4.75：t：4)(5.29：t：4)
(3)TG-DTA
(Ar：100ml/min、升溫：10℃/min、樣品量：11.349mg)
減少50質量%時之溫度：259℃
藉由目視，對化合物No.6、19、27、30、40及以下所示之比較化合物1觀察常壓20℃下之化合物之狀態，對於固體化合物，使用DSC(Differential Scanning Calorimetry，示差掃描熱析法)測定裝置測定熔點，進而測定TG-DTA(常壓，Ar流量：100ml/min，升溫：10℃/min)，藉此測定減少50質量%時之溫度(以下，有時略寫為50%T)及加熱至400℃時減少之質量%(以下，有時略寫為400wt)。將結果示於表1。
根據表1之結果，可知評價例1-1~1-5較之比較例1，熔點大幅降低，尤其是1-3~1-5於未達20℃之條件下為液體之化合物。熔點較低之化合物容易穩定地以液體狀態供給原料，故而作為氣相化學成長法用原料具有優勢。又，關於50%T，可知評價例1-1~1-5與比較例1相比並無較大差異，蒸氣壓大致同等。又，比較例1於加熱至400℃時發生熱分解，而產生大量之殘分，與此相對，評價例1-1~1-5於加熱至400℃時因熱分解產生之殘分非常少。
將化合物No.19作為化學氣相成長用原料，使用圖1所示之裝置，藉由以下條件之ALD法於矽晶圓上製造氧化鉬薄膜。對所得之薄膜進行利用X射線反射率法之膜厚測定及利用X射線光電子分光法之薄膜組成之確認，結果膜厚為1.5nm，膜組成係氧化鉬(MoOx，x=2~3)，碳含量少於檢測下限之0.1atom%。每次循環所得之膜厚為0.03nm。
(條件)
反應溫度(基體溫度)：280℃；反應性氣體：臭氧氣體
(步驟)
將包含下述(1)~(4)之一系列步驟設為1次循環，重複進行50次循
環。
(1)導入於原料容器溫度90℃、原料容器內壓力70Pa之條件下氣化所成之化學氣相成長用原料之蒸氣，於系統壓力100Pa下沈積10秒。
(2)藉由15秒之氬氣吹拂去除未反應原料。
(3)導入反應性氣體，於系統壓力100Pa下反應10秒。
(4)藉由15秒之氬氣吹拂去除未反應原料。
Claims (6)
- 一種薄膜之製造方法，其係將使含有下述通式(I)所表示之鉬醯亞胺化合物而成之薄膜形成用原料氣化而獲得的含有鉬醯亞胺化合物之蒸氣導入至基體上，使其分解及/或進行化學反應，而於基體上形成含有鉬之薄膜，
- 如請求項1之薄膜之製造方法，其中上述通式(I)所表示之鉬醯亞胺化合物係以下述通式(II)所表示，
- 一種薄膜形成用原料，其係用於如請求項1之薄膜之製造方法的 含有下述通式(I)所表示之鉬醯亞胺化合物而成者，
- 如請求項3之薄膜形成用原料，其中上述通式(I)所表示之鉬醯亞胺化合物係以下述通式(II)所表示，
- 一種鉬醯亞胺化合物，其係以下述通式(II)所表示，
- 如請求項5之鉬醯亞胺化合物，其中R22及R23為甲基，R24為乙基或新戊基。
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| US11390638B1 (en) | 2021-01-12 | 2022-07-19 | Applied Materials, Inc. | Molybdenum(VI) precursors for deposition of molybdenum films |
| US11459347B2 (en) | 2021-01-12 | 2022-10-04 | Applied Materials, Inc. | Molybdenum(IV) and molybdenum(III) precursors for deposition of molybdenum films |
| US11434254B2 (en) | 2021-01-12 | 2022-09-06 | Applied Materials, Inc. | Dinuclear molybdenum precursors for deposition of molybdenum-containing films |
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