WO2023200429A1 - Niobium vanadium, tantalum film forming compositions and deposition of group v (five) containing films using the same - Google Patents
Niobium vanadium, tantalum film forming compositions and deposition of group v (five) containing films using the same Download PDFInfo
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- WO2023200429A1 WO2023200429A1 PCT/US2022/024416 US2022024416W WO2023200429A1 WO 2023200429 A1 WO2023200429 A1 WO 2023200429A1 US 2022024416 W US2022024416 W US 2022024416W WO 2023200429 A1 WO2023200429 A1 WO 2023200429A1
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- 239000000203 mixture Substances 0.000 title claims abstract description 89
- 229910052715 tantalum Inorganic materials 0.000 title claims abstract description 16
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 230000008021 deposition Effects 0.000 title claims description 34
- ABLLXXOPOBEPIU-UHFFFAOYSA-N niobium vanadium Chemical compound [V].[Nb] ABLLXXOPOBEPIU-UHFFFAOYSA-N 0.000 title 1
- 239000010955 niobium Substances 0.000 claims abstract description 873
- 238000000034 method Methods 0.000 claims abstract description 71
- 239000002243 precursor Substances 0.000 claims abstract description 66
- 239000000758 substrate Substances 0.000 claims abstract description 65
- 239000000376 reactant Substances 0.000 claims abstract description 46
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 26
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000005019 vapor deposition process Methods 0.000 claims abstract description 9
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 8
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000005103 alkyl silyl group Chemical group 0.000 claims abstract description 7
- 125000003800 germyl group Chemical group [H][Ge]([H])([H])[*] 0.000 claims abstract description 7
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims abstract description 5
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 35
- 230000008569 process Effects 0.000 claims description 32
- 238000010926 purge Methods 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 14
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 13
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 239000011261 inert gas Substances 0.000 claims description 11
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 10
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 claims description 6
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 6
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 claims description 6
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 3
- 229910015148 B2H6 Inorganic materials 0.000 claims description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 3
- 229910014329 N(SiH3)3 Inorganic materials 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 239000010406 cathode material Substances 0.000 claims description 3
- VGYDTVNNDKLMHX-UHFFFAOYSA-N lithium;manganese;nickel;oxocobalt Chemical compound [Li].[Mn].[Ni].[Co]=O VGYDTVNNDKLMHX-UHFFFAOYSA-N 0.000 claims description 3
- 229910001317 nickel manganese cobalt oxide (NMC) Inorganic materials 0.000 claims description 3
- 239000007800 oxidant agent Substances 0.000 claims description 3
- 229910007264 Si2H6 Inorganic materials 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 239000010408 film Substances 0.000 description 133
- 239000010410 layer Substances 0.000 description 50
- 238000000231 atomic layer deposition Methods 0.000 description 49
- 238000000151 deposition Methods 0.000 description 35
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 25
- 229910052751 metal Inorganic materials 0.000 description 21
- 239000002184 metal Substances 0.000 description 21
- 235000012431 wafers Nutrition 0.000 description 21
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 18
- 239000000463 material Substances 0.000 description 18
- 150000001875 compounds Chemical class 0.000 description 14
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 14
- 239000012159 carrier gas Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000007789 gas Substances 0.000 description 12
- 229910052744 lithium Inorganic materials 0.000 description 11
- -1 Cp2Nb(H)(CO) Chemical class 0.000 description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 10
- 238000000137 annealing Methods 0.000 description 10
- 238000005229 chemical vapour deposition Methods 0.000 description 10
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 10
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000012535 impurity Substances 0.000 description 8
- 229910052710 silicon Inorganic materials 0.000 description 8
- 239000010703 silicon Substances 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 238000005137 deposition process Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 6
- 229910052720 vanadium Inorganic materials 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 229910021478 group 5 element Inorganic materials 0.000 description 5
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 230000005587 bubbling Effects 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 125000006165 cyclic alkyl group Chemical group 0.000 description 4
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 238000002411 thermogravimetry Methods 0.000 description 4
- 230000008016 vaporization Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical class C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 229910003327 LiNbO3 Inorganic materials 0.000 description 3
- 229910021542 Vanadium(IV) oxide Inorganic materials 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000003990 capacitor Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 229910052732 germanium Inorganic materials 0.000 description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 3
- 229910052735 hafnium Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- LZWQNOHZMQIFBX-UHFFFAOYSA-N lithium;2-methylpropan-2-olate Chemical compound [Li+].CC(C)(C)[O-] LZWQNOHZMQIFBX-UHFFFAOYSA-N 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 229910000484 niobium oxide Inorganic materials 0.000 description 3
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 3
- 150000004767 nitrides Chemical class 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000011591 potassium Chemical class 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical compound O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 description 3
- 239000012808 vapor phase Substances 0.000 description 3
- 238000009834 vaporization Methods 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical class CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 229910019704 Nb2O Inorganic materials 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000001505 atmospheric-pressure chemical vapour deposition Methods 0.000 description 2
- CFJRGWXELQQLSA-UHFFFAOYSA-N azanylidyneniobium Chemical compound [Nb]#N CFJRGWXELQQLSA-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 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
- 230000015572 biosynthetic process Effects 0.000 description 2
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- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-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
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 230000001627 detrimental effect Effects 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- NQKXFODBPINZFK-UHFFFAOYSA-N dioxotantalum Chemical compound O=[Ta]=O NQKXFODBPINZFK-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910021480 group 4 element Inorganic materials 0.000 description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 2
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- 229930195733 hydrocarbon Natural products 0.000 description 2
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- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
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- 150000002602 lanthanoids Chemical class 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 238000004518 low pressure chemical vapour deposition Methods 0.000 description 2
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- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
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- JKOSHCYVZPCHSJ-UHFFFAOYSA-N benzene;toluene Chemical compound C1=CC=CC=C1.C1=CC=CC=C1.CC1=CC=CC=C1 JKOSHCYVZPCHSJ-UHFFFAOYSA-N 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 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 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- CEJLBZWIKQJOAT-UHFFFAOYSA-N dichloroisocyanuric acid Chemical compound ClN1C(=O)NC(=O)N(Cl)C1=O CEJLBZWIKQJOAT-UHFFFAOYSA-N 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001227 electron beam curing Methods 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000001030 gas--liquid chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- KQHQLIAOAVMAOW-UHFFFAOYSA-N hafnium(4+) oxygen(2-) zirconium(4+) Chemical compound [O--].[O--].[O--].[O--].[Zr+4].[Hf+4] KQHQLIAOAVMAOW-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000012705 liquid precursor Substances 0.000 description 1
- GSPVGSMROLCBGA-UHFFFAOYSA-N lithium;2,2,6,6-tetramethylheptane-3,5-dione Chemical compound [Li].CC(C)(C)C(=O)CC(=O)C(C)(C)C GSPVGSMROLCBGA-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000007726 management method Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- HFLAMWCKUFHSAZ-UHFFFAOYSA-N niobium dioxide Inorganic materials O=[Nb]=O HFLAMWCKUFHSAZ-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- AOLPZAHRYHXPLR-UHFFFAOYSA-I pentafluoroniobium Chemical compound F[Nb](F)(F)(F)F AOLPZAHRYHXPLR-UHFFFAOYSA-I 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003217 pyrazoles Chemical class 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000004151 rapid thermal annealing Methods 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical group [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 1
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 1
- HSXKFDGTKKAEHL-UHFFFAOYSA-N tantalum(v) ethoxide Chemical compound [Ta+5].CC[O-].CC[O-].CC[O-].CC[O-].CC[O-] HSXKFDGTKKAEHL-UHFFFAOYSA-N 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 230000007723 transport mechanism Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 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
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
- 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
- C23C16/40—Oxides
- C23C16/405—Oxides of refractory metals or yttrium
Definitions
- the present invention relates to Group V (five)-containing film forming compositions, methods of synthesizing the same, and methods of using the same to deposit Group V-containing films on substrates via vapor deposition processes.
- the Group V- containing film forming composition comprises a precursor having the formula: wherein M is Group V (five) element, vanadium (V), niobium (Nb), or tantalum (Ta);
- Halides such as CpNbCl 4 (CAS 33114-1507), NbF 5 , NbBr 5 (Thin solid films, 1981 , 79, 75), NbCI 5 (Crystal growth, 1978, 45, 37) and TaCI 5 (US 6,268,288), have been widely investigated.
- some by-products generated during the deposition process such as HCI or CI 2 , cause surface/interface roughness that can be detrimental to the final films.
- Cl or F impurities are detrimental to the final electrical properties. It is therefore expected to find new compounds having sufficient volatility but without containing Cl, F, or Br atoms.
- Group V (five) precursors have been considered to enable such deposition.
- Alkoxides such as penta-ethoxy-tantalum (PET) are widely used and disclosed.
- PET penta-ethoxy-tantalum
- the same problem is observed for compounds such as Cp2Nb(H)(CO), CpNb(CO) 4 (J. Organomet. Chem., 557 (1998) 77-92), V(CO) 6 (Thermochimica Acta, 1984, 75, 71), ( ⁇ 5 -C 5 H 5 )V(CO) 4 (M. L. Green, R. A. Levy, J. Metals 37 (1985) 63).
- US 6,368,398 discloses another improvement with the use for instance of Ta[OC(O)C(CH 3 )3]5, however with the same limitation as disclosed here above.
- WO 2002/20870 discloses the deposition of Ta 2 O 5 use using tert- butylimido(tris(diethylamido)tantalum (TBTDET).
- US 6,593,484 and US 2004/0219784 disclose a method of deposition of tantalum nitride films by sequential injection of TBTDET or tertiary amyl imido-tris-dimethylamido tantalum (Ta(NC(CH 3 ) 2 C 2 H 5 )(N(CH 3 )2) 3 (TAI MATA) and other N source.
- US 6,379,748 discloses Ta(Me 3 SiCp) 2 H 3 , which is a biscyclopentadienyl Ta hydride and is a solid having a low volatility.
- a method for forming a Group V (five)-containing film comprising the steps of: a) exposing a substrate to a vapor of a Group V (five)-containing film forming composition; b) exposing the substrate to a co-reactant; and c) repeating the steps of a) and b) until a desired thickness of the Group V (five)- containing film is deposited on the substrate using a vapor deposition process, wherein the Group V (five)-containing film forming composition comprises a precursor having the formula: wherein M is Group V (five) element, vanadium (V), niobium (Nb), or tantalum (Ta);
- the disclosed methods may include one or more of the following aspects:
- the co-reactant being selected from the group consisting of O 2 , O 3 , H 2 O, H2O2, NO, N 2 O, NO2, oxygen radicals thereof, and mixtures thereof;
- the co-reactant being selected from the group consisting of H 2 , H 2 CO, N 2 H 4 , NH 3 , an amine, a hydrazine N(SiH 3 )3, B 2 H 6 , Si 2 H s radicals thereof, and mixtures thereof;
- MeCp)Nb( NtBu)(nPentyl 2 ⁇ EDA) > (Di-MeCp)Nb( ⁇ NtBu)(tAm 2 -EDA),
- the Group V (five)-containing film being an Nb 2 O 5 film or an NbN film;
- the substrate being a Si wafer; « the substrate being a crystalline silicon layer;
- the substrate being a powder substrate
- the vapor deposition process being an ALD process or a CVD process
- the vapor deposition process being a PEALD process or a spatial ALD process
- a deposition temperature ranging from approximately 50°C and approximately 600°C.
- a Group V (five)-containing film forming composition for a vapor deposition process comprising a precursor having the formula: wherein M is Group V (five) element, vanadium (V), niobium (Nb), or tantalum (Ta);
- the disclosed methods may include one or more of the following aspects:
- R 1 to R 8 each being independently H, Me, Et, nPr, IPr, tBu, sBu, IBu, nBu, tAmyl, SiMe 3 , SiMe 2 H, or SiH 2 Me;
- the Group V (five)-containing film forming composition comprising between approximately 95% w/w and approximately 100.0% w/w of the precursor;
- the Group V (five)-containing film forming composition comprising between 99,0% w/w to 100.0% w/w of the precursor;
- the Group V (five)-containing film forming composition comprising between approximately 0.0% w/w and approximately 5.0% w/w impurities.
- the disclosed methods may include one or more of the following aspects:
- NMC Lithium Nickel Manganese Cobalt Oxide
- LCO Lithium Cobalt Oxide
- LFP Lithium Iron Phosphate
- room temperature in the text or in a claim means from approximately 20°C to approximately 30°C.
- ambient temperature refers to an environment temperature approximately 20°C to approximately 30°C.
- substrate refers to a material or materials on which a process Is conducted.
- the substrate may refer to a wafer having a material or materials on which a process is conducted.
- the substrates may be any suitable wafer used in semiconductor, photovoltaic, flat panel, or LCD-TFT device manufacturing.
- the substrate may also have one or more layers of differing materials already deposited upon it from a previous manufacturing step.
- the wafers may include silicon layers (e.g., crystalline, amorphous, porous, etc.), silicon containing layers (e.g., SiO 2 , SiN, SiON, SiCOH, etc.), metal containing layers (e.g., copper, cobalt, ruthenium, tungsten, platinum, palladium, nickel, ruthenium, gold, etc.) or combinations thereof.
- the substrate may be planar or patterned.
- the substrate may be an organic patterned photoresist film.
- the substrate may include layers of oxides which are used as dielectric materials in MEMS, 3D NAND, MIM, DRAM, or FeRam device applications (for example, ZrO 2 based materials, HfO 2 based materials, TIO 2 based materials, AI2O 3 based materials, rare earth oxide based materials, ternary oxide based materials, etc.) or nitride-based films (for example, TaN, TiN, NbN) that are used as electrodes.
- oxides which are used as dielectric materials in MEMS, 3D NAND, MIM, DRAM, or FeRam device applications
- ZrO 2 based materials for example, ZrO 2 based materials, HfO 2 based materials, TIO 2 based materials, AI2O 3 based materials, rare earth oxide based materials, ternary oxide based materials, etc.
- nitride-based films for example, TaN, TiN, NbN
- wafer or “patterned wafer” refers to a wafer having a stack of films on a substrate and at least the top-most film having topographic features that have been created in steps prior to the deposition of the Group V (five)-containing film.
- the term “aspect ratio” refers to a ratio of the height of a trench (or aperture) to the width of the trench (or the diameter of the aperture).
- high aspect ratio refers to an aspect ratio larger than approximately 2:1 , preferably an aspect ratio ranging from approximately 2:1 to approximately 200:1.
- film and “layer” may be used interchangeably. It is understood that a film may correspond to, or related to a layer, and that the layer may refer to the film. Furthermore, one of ordinary skill in the art will recognize that the terms “film” or “layer used herein refer to a thickness of some material laid on or spread over a surface and that the surface may range from as large as the entire wafer to as small as a trench or a line. [0024] Note that herein, the terms “aperture”, “via”, “hole” and “trench” may be used interchangeably to refer to an opening formed in a semiconductor structure.
- NAND refers to a “Negative AND” or “Not AND” (electronic logic gate);
- the abbreviation “2D” refers to 2 dimensional gate structures on a planar substrate;
- the abbreviation “3D” refers to 3 dimensional or vertical gate structures, wherein the gate structures are stacked In the vertical direction.
- a substrate temperature may correspond to, or be related to a deposition temperature, and that the deposition temperature may refer to the substrate temperature.
- the term “film-forming composition” refers to a composition used for deposition of a film.
- the film-forming composition may include, but Is not limited to, a precursor, a solvent and/or a carrier gas.
- the film-forming composition may include, but is not limited to, a precursor, optionally a solvent, optionally a carrier gas, and optionally one or more co- reactant(s).
- the precursor may be supplied either in a neat form or in a blend with a suitable solvent.
- the precursor may be present in varying concentrations in the solvent.
- the precursor may be vaporized by passing a carrier gas into a container that contains the precursor or by bubbling the carrier gas into the precursor.
- the carrier gas and precursor are then introduced into a reactor as a vapor.
- the co-reactant may be an oxidizer, a reducing agent, a dilute gas, an additive, an inhibitor, an additional or a secondary precursor, etc., for assisting in formation of the film.
- an inert gas selected from N 2 , He, Ar, Kr, Xe may be used as the carrier gas and/or the dilute gas.
- precursor and “deposition compound” and “deposition gas” may be used interchangeably when the precursor is in a gaseous state at room temperature and ambient pressure, it is understood that a precursor may correspond to, or be related to a deposition compound or deposition gas, and that the deposition compound or deposition gas may refer to the precursor.
- hydrocarbon refers to a saturated or unsaturated function group containing exclusively carbon and hydrogen atoms.
- alkyl group refers to saturated functional groups containing exclusively carbon and hydrogen atoms.
- An alkyl group is one type of hydrocarbon.
- alkyl group refers to linear, branched, or cyclic alkyl groups. Examples of linear alkyl groups include without limitation, methyl groups, ethyl groups, propyl groups, butyl groups, etc. Examples of branched alkyls groups include without limitation, t-butyl.
- cyclic alkyl groups include without limitation, cyclopropyl groups, cyclopentyl groups, cyclohexyl groups, etc.
- alkyl group refers to saturated functional groups containing exclusively carbon and hydrogen atoms.
- alkyl group refers to linear, branched, or cyclic alkyl groups. Examples of linear alkyl groups include without limitation, methyl groups, ethyl groups, propyl groups, butyl groups, etc. Examples of branched alkyls groups include without limitation, t-butyl.
- cyclic alkyl groups include without limitation, cyclopropyl groups, cyclopentyl groups, cyclohexyl groups, etc.
- the abbreviation “Me” refers to a methyl group
- the abbreviation “Et” refers to an ethyl group
- the abbreviation “Pr” refers to a propyl group
- the abbreviation “nPr” refers to a “normal” or linear propyl group
- the abbreviation “IPr” refers to an isopropyl group
- the abbreviation “Bu” refers to a butyl group
- the abbreviation “nBu” refers to a “normal” or linear butyl group
- the abbreviation “tBu” refers to a tert-butyl group, also known as 1 ,1- dimethylethyl
- the abbreviation “sBu” refers to a sec-butyl group, also known as
- R groups independently selected relative to other R groups bearing the same or different subscripts or superscripts, but is also independently selected relative to any additional species of that same R group.
- MR 1 (NR 2 R 3 ) (4-x:)
- x is 2 or 3
- the two or three R 1 groups may, but need not be identical to each other or to R 2 or to R 3 .
- values of R groups are independent of each other when used in different formulas.
- exemplary is used herein to mean serving as an example, instance, or illustration. Any aspect or design described herein as “exemplary” is not necessarily to be construed as preferred or advantageous over other aspects or designs. Rather, use of the word exemplary is intended to present concepts in a concrete fashion.
- the term "or” is intended to mean an inclusive “or” rather than an exclusive “or”. That is, unless specified otherwise, or clear from context, “X employs A or B” is intended to mean any of the natural inclusive permutations. That is, if X employs A; X employs B; or X employs both A and B, then “X employs A or B” is satisfied under any of the foregoing instances.
- the articles “a” and “an” as used in this application and the appended claims should generally be construed to mean “one or more” unless specified otherwise or clear from context to be directed to a singular form.
- “Comprising” in a claim is an open transitional term which means the subsequently identified claim elements are a nonexclusive listing (i.e., anything else may be additionally included and remain within the scope of “comprising”). “Comprising” is defined herein as necessarily encompassing the more limited transitional terms “consisting essentially of” and “consisting of; “comprising” may therefore be replaced by “consisting essentially of or “consisting of” and remain within the expressly defined scope of “comprising”.
- Providing in a claim is defined to mean furnishing, supplying, making available, or preparing something. The step may be performed by any actors in the absence of express language in the claim to the contrary.
- FIG. 4a is a full image of step coverage of patterned wafer of Nb 2 O 5 film at 325°C by SEM;
- FIG. 4b is a top image of FIG. 4a
- FIG. 4c is a bottom image of FIG. 4a.
- FIG. 5 is a XPS depth profile plot of Nb 2 O 5 film at 325°C.
- Group V (five) (V, Nb, Ta) metal containing films forming compositions methods of synthesizing the same, and methods of forming Group V metal containing films on one or more substrates via ALD (atomic layer deposition processes) using the Group V metal containing film forming compositions.
- the disclosed Group V element-containing film forming compositions comprise Group V element-containing precursors having the formula:
- M is Group V (five) element, vanadium (V), niobium (Nb), or tantalum (Ta);
- R 1 to R 8 each is H, a C1-C5 alkyl group, a fluoro group, an alkylsilyl group, a germyl group, an alkylamide or an alkylsilylamide;
- m 1 to 5, n ⁇ 1 to 5.
- the nitrogen atoms and a cyclopentadienyl ring may be bonded to the center Group V atom M, resulting in a tetracoordinate M(V) center.
- the resulting geometry may be pseudo tetrahedral.
- R 3 ’ 7 represents R 3 R 4 R 5 R 5 R 7 .
- R 3 ' 7 represents R 3 R 4 R 5 R 6 R 7 .
- the disclosed precursors have the flowing advantages.
- the disclosed precursors have high thermal stability, so that a high deposition temperature and a broad ALD window are expected, in addition, the disclosed precursors are liquid precursors and therefore easier for vaporization and vapor delivery.
- Purity of the disclosed Group V-containing film forming composition is greater than 95% w/w (i.e. , 95.0% w/w to 100.0% w/w), preferably greater than 98% w/w (i.e. , 98.0% w/w to 100.0% w/w), and more preferably greater than 99% w/w (i.e., 99.0% w/w to 100.0% w/w).
- 95% w/w i.e. , 95.0% w/w to 100.0% w/w
- 98% w/w i.e. , 98.0% w/w to 100.0% w/w
- 99% w/w i.e., 99.0% w/w to 100.0% w/w.
- the disclosed Group V-containing film forming compositions may contain any of the following impurities: pyrazoles; pyridines; alkylamines; alkylimines; THF; ether; pentane; cyclohexane; heptanes; benzene; toluene: chlorinated metal compounds; lithium, sodium, potassium pyrazolyl.
- the total quantity of these impurities is preferably below 5% w/w (i.e., 0.0% w/w to 5.0% w/w), preferably below 2% w/w (i.e., 0.0% w/w to 2.0% w/w), and more preferably below 1 % w/w (i.e., 0.0% w/w to 1.0% w/w).
- the composition may be purified by recrystallisation, sublimation, distillation, and/or passing the gas liquid through a suitable adsorbent, such as a 4A molecular sieve.
- metal impurities may include, but are not limited to, Aluminum (Al), Arsenic (As), Barium (Ba), Beryllium (Be), Bismuth (Bi), Cadmium (Cd), Calcium (Ca), Chromium (Cr), Cobalt (Co), Copper (Cu), Gallium (Ga), Germanium (Ge), Hafnium (Hf), Zirconium (Zr), Indium (In), Iron (Fe), Lead (Pb), Lithium (Li), Magnesium (Mg), Manganese (Mn), Tungsten (W), Nickel (Ni), Potassium (K), Sodium (Na), Strontium (Sr), Thorium (Th), Tin (Sn), Titanium (Ti), Uranium (U), and Zinc (Z
- the disclosed Group V-containing film forming compositions are suitable for atomic layer deposition (ALD). More particularly, the disclosed Group V-containing film forming compositions are capable of surface saturation, self limited growth per cycle, and perfect step coverage on aspect ratios ranging from approximately 2:1 to approximately 200:1 , and preferably from approximately 20:1 to approximately 100:1. Additionally, the disclosed Group V-containing film forming compositions have high decomposition temperatures, indicating good thermal stability to enable ALD. The high decomposition temperatures permit ALD at higher temperatures, resulting in films having higher purity.
- the disclosed method may be useful in the manufacture of semiconductor, photovoltaic, LCD-TFT, flat panel type devices.
- the disclosed Group V-containing film forming compositions may be used to deposit Group V-containing films using any deposition methods known to those of skill in the art. Examples of suitable vapor deposition methods include chemical vapor deposition (CVD) atomic layer deposition (ALD).
- CVD chemical vapor deposition
- ALD atomic layer deposition
- Exemplary CVD methods include thermal CVD, plasma enhanced CVD (PECVD), pulsed CVD (PCVD), low pressure CVD (LPCVD), sub-atmospheric CVD (SACVD) atmospheric pressure CVD (APCVD), hot-wire CVD (HWCVD, also known as cat-CVD, in which a hot wire serves as an energy source for the deposition process), radicals incorporated CVD, and combinations thereof.
- Exemplary ALD methods include thermal ALD, plasma enhanced ALD (PEALD), spatial ALD, hot-wire ALD (HWALD), radicals incorporated ALD, and combinations thereof, Super critical fluid deposition may also be used.
- the deposition method is preferably ALD, PE-ALD, spatial ALD in order to provide suitable step coverage and film thickness control
- the disclosed Group V-containing film forming compositions may be supplied either in neat form in a blend with a suitable solvent, such as ethyl benzene, xylene, mesitylene, decalin, decane, dodecane.
- a suitable solvent such as ethyl benzene, xylene, mesitylene, decalin, decane, dodecane.
- the disclosed precursors may be present in varying concentrations in the solvent.
- the neat blended Group V-containing film forming compositions are introduced into a reactor in vapor form by conventional means, such as tubing and/or flow meters.
- the vapor form may be produced by vaporizing the neat blended composition through a conventional vaporization step such as direct vaporization, distillation, by bubbling, or by using a sublimator.
- the neat blended composition may be fed in liquid state to a vaporizer where it is vaporized before it is introduced into the reactor.
- the neat blended composition may be vaporized by passing a carrier gas into a container containing the composition by bubbling the carrier gas into the composition.
- the carrier gas may include, but is not limited to, Ar, He, N 2 , and mixtures thereof. Bubbling with a carrier gas may also remove any dissolved oxygen present in the neat blended composition.
- the carrier gas and composition are then introduced into the reactor as a vapor,
- the container containing the disclosed Group V-containing film forming composition may be heated to a temperature that permits the composition to be in its liquid phase and to have a sufficient vapor pressure.
- the container may be maintained at temperatures in the range of, for example, approximately 0°C to approximately 200°C. Those skilled in the art recognize that the temperature of the container may be adjusted in a known manner to control the amount of precursor vaporized.
- the reactor may be any enclosure chamber within a device in which deposition methods take place such as without limitation, a parallel-plate type reactor, a cold-wall type reactor, a hot-wall type reactor, a single-wafer reactor, a multi-wafer reactor, a powder ALD reactor, other types of deposition systems under conditions suitable to cause the compounds to react and form the layers.
- a parallel-plate type reactor such as without limitation, a parallel-plate type reactor, a cold-wall type reactor, a hot-wall type reactor, a single-wafer reactor, a multi-wafer reactor, a powder ALD reactor, other types of deposition systems under conditions suitable to cause the compounds to react and form the layers.
- a parallel-plate type reactor such as without limitation, a parallel-plate type reactor, a cold-wall type reactor, a hot-wall type reactor, a single-wafer reactor, a multi-wafer reactor, a powder ALD reactor, other types of deposition systems under conditions suitable to cause the compounds to react and
- the reactor contains one more substrates onto which the films will be deposited.
- a substrate is generally defined as the material on which a process is conducted.
- the substrates may be any suitable substrate used in semiconductor, photovoltaic, fiat panel, LCD-TFT device manufacturing.
- suitable substrates include wafers, such as silicon, silica, glass, GaAs wafers.
- the wafer may have one more layers of differing materials deposited on it from a previous manufacturing step.
- the wafers may include a dielectric layer.
- the wafers may include silicon layers (crystalline, amorphous, porous, etc,), silicon oxide layers, silicon nitride layers, silicon oxy nitride layers, carbon doped silicon oxide (SiCOH) layers, metal, metal oxide, metal nitride layers (Ti, Ru, Ta, etc,) combinations thereof. Additionally, the wafers may include copper layers noble metal layers (e.g., platinum, palladium, rhodium, and gold). Plastic layers, such as poly(3,4- ethylenedioxythiophene)poly(styrenesulfonate)[PEDOT:PSS] may also be used. The layers may be planar or patterned.
- the disclosed processes may deposit the Group V-containing layer directly on the wafer or directly on one or more layers on top of the wafer (when patterned layers form the substrate).
- film layer
- the terms “film” “layer” used herein refer to a thickness of some material laid on spread over a surface and that the surface may be a trench a line.
- substrates the wafer and any associated layers thereon are referred to as substrates.
- a Niobium oxide film may be deposited onto a metal oxide layer, such as a ZrO 2 layer, an HfO 2 layer, an AI2O 3 layer, a MoOs layer.
- Niobium oxide layer may be deposited on the Niobium oxide layer to form a nanolaminate; for example, ZrO 2 /Nb 2 O/ZrO 2 laminate dielectric stack are typical of DRAM high-k stack.
- a conductive metal nitride layer such as a Niobium Nitride layer or a Titanium Nitride layer, may be deposited before on the last metal oxide layer to form, respectively, the bottom and top electrodes.
- the resulting NbN/ZrO 2 /Nb 2 O/ZrO 2 /NbN stack may be used in DRAM capacitors.
- Other conductive films, such as RuO, Ru, Pt, Ir, WN, WNC may be also used as the bottom top electrodes, alone in addition to the NbN or TaN layers.
- the substrate may also be a powder, such as the powder used in rechargeable battery technology.
- powder materials include NMC (Lithium Nickel Manganese Cobalt Oxide), LCO (Lithium Cobalt Oxide), LFP (Lithium Iron Phosphate), and other battery cathode materials.
- the temperature and the pressure within the reactor are held at conditions suitable for ALD.
- conditions within the chamber are such that at least part of the precursor is deposited onto the substrate to form a Group V (five)-containing layer.
- the pressure in the reactor or the deposition pressure may be held between about 10 -3 torr and about 100 Torr, more preferably between about 10 -2 and 100 Torr, as required per the deposition parameters.
- the temperature in the reactor or the deposition temperature may be held between about 100°C and about 600°C, preferably between about 150°C and about 500°C.
- “at least part of the precursor is deposited” means that some all of the precursor reacts with adheres to the substrate.
- the temperature of the reactor may be controlled by either controlling the temperature of the substrate holder controlling the temperature of the reactor wall. Devices used to heat the substrate are known in the art.
- the reactor wall is heated to a sufficient temperature to obtain the desired film at a sufficient growth rate and with desired physical state and composition.
- a non-limiting exemplary temperature range to which the reactor wall may be heated includes from approximately 50°C to approximately 600°C.
- the deposition temperature may range from approximately 50°C to approximately 500°C, preferably, from approximately 100°C to approximately 500°C 1 more preferably, from approximately 150°C to approximately 500°C.
- the deposition temperature may range from approximately 10CTC to approximately 600° C.
- a coreactant may be introduced into the reactor.
- the coreactant may be H 2 , H 2 CO, N 2 H 4 , NH 3 , a primary amine, a secondary amine, a tertiary amine, trisilylamine, a hydrazine N(SiH 3 )3, B 2 H 6 6 Si 2 H 6 , radicals thereof, and mixtures thereof.
- the co-reactant is H 2 /NH 3 .
- the co-reactant when the target is a dielectric film, the co-reactant may be an oxidizing gas such as one of O 2 , O 3 , H 2 O, H 2 O 2 , NO, N 2 O, NO 2 , oxygen containing radicals such as O- OH-, carboxylic acids, formic acid, acetic acid, propionic acid, and mixtures thereof.
- the oxidizing gas is selected from the group consisting of O 3 , H 2 O 2 H 2 O.
- the co-reactant may be treated by a plasma, in order to decompose the reactant into its radical form, N 2 may also be utilized as a nitrogen source gas when treated with plasma.
- the plasma may be generated with a power ranging from about 10 W to about 1000 W, preferably from about 50 W to about 500 W.
- the plasma may be generated present within the reactor itself.
- the plasma may generally be at a location removed from the reactor, for instance, in a remoteiy iocated plasma system.
- One of skill in the art will recognize methods and apparatus suitable for such plasma treatment.
- the co-reactant may be introduced into a direct plasma reactor, which generates plasma in the reaction chamber, to produce the plasma-treated reactant in the reaction chamber.
- direct plasma reactors include the TitanTM PECVD System produced by Trion Technologies.
- the co-reactant may be introduced and held in the reaction chamber prior to plasma processing. Alternatively, the plasma processing may occur simultaneously with the introduction of the reactant.
- In-situ plasma is typically a 13.56 MHz RF inductively coupled plasma that is generated between the showerhead and the substrate holder.
- the substrate the showerhead may be the powered electrode depending on whether positive ion impact occurs.
- Typical applied powers In in-situ plasma generators are from approximately 30 Wto approximately 1000 W.
- powers from approximately 30 W to approximately 600 W are used in the disclosed methods. More preferably, the powers range from approximately 100 W to approximately 500 W.
- the disassociation of the coreactant using in-situ plasma is typically less than achieved using a remote plasma source for the same power input and is therefore not as efficient in reactant dissociation as a remote plasma system, which may be beneficial for the deposition of Group V (five)-containing films on substrates easily damaged by plasma.
- the plasma-treated co-reactant may be produced outside of the reaction chamber, for example, a remote plasma to treat the co-reactant prior to passage into the reaction chamber.
- the ALD conditions within the chamber allow the disclosed Group V-containing film forming composition adsorbed chemisorbed on the substrate surface to react and form a Group V-containing film on the substrate.
- plasma-treating the co-reactant may provide the co-reactant with the energy needed to react with the disclosed Group V-containing film forming composition.
- an additional precursor compound may be introduced Into the reactor.
- the additional precursor may be used to provide additional elements to the Group V-containing film.
- the additional elements may include Group I elements (lithium, Sodium, potassium), lanthanides (Ytterbium, Erbium, Dysprosium, Gadolinium, Praseodymium, Cerium, Lanthanum, Yttrium), Group IV elements (zirconium, titanium, hafnium), main group elements (germanium, silicon, aluminium), additional different Group V elements, and mixtures thereof.
- the resultant film deposited on the substrate contains the Group V metal in combination with an additional element.
- the additional precursor and the Group V precursors are used in more than one ALD super cycle sequences, a nanolaminate film is obtained.
- the Group V- containing film will contain Li, such as, a lithium noibiate (LiNbO 3 ) film.
- Li such as, a lithium noibiate (LiNbO 3 ) film.
- the Group V-containing films containing Li may be formed by ALD on any types of substrates including a powder.
- the Group V-containing film forming composition and co-reactants may be introduced into the reactor sequentially (i.e. , ALD).
- the reactor may be purged with an inert gas (e.g., N 2 , He, Ar, Kr, or Xe ) between the introduction of each of the Group V-containing film forming composition, any additional precursors, and the co-reactants.
- an inert gas e.g., N 2 , He, Ar, Kr, or Xe
- Another example is to introduce the co-reactant continuously and to introduce the Group V-containing film forming composition by pulse, while activating the co-reactant sequentially with a plasma, provided that the Group V-containing film forming composition and the non-activated co- reactant do not substantially react at the chamber temperature and pressure conditions (CW PEALD).
- CW PEALD chamber temperature and pressure conditions
- Each pulse of the disclosed Group V-containing film forming composition may last for a time period ranging from about 0.01 seconds to about 120 seconds, alternatively from about 1 seconds to about 80 seconds, alternatively from about 5 seconds to about 30 seconds.
- the co-reactant may also be pulsed into the reactor, in such embodiments, the pulse of each may last for a time period ranging from about 0.01 seconds to about 120 seconds, alternatively from about 1 seconds to about 30 seconds, alternatively from about 2 seconds to about 20 seconds.
- the vaporized Group V-containing film forming compositions and co-reactants may be simultaneously sprayed from different sectors of a shower head (without mixing of the composition and the reactant) under which a susceptor holding several wafers is spun (spatial ALD).
- deposition may take place for a varying length of time. Generally, deposition may be allowed to continue as long as desired necessary to produce a film with the necessary properties. Typical film thicknesses may vary from several angstroms to several hundreds of microns, and typically from 2 to 100 nm, depending on the specific deposition process. The deposition process may also be performed as many times as necessary to obtain the desired film.
- the vapor phase of the disclosed Group V-containing film forming composition is introduced into the reactor, where it is contacted with a suitable substrate. Excess composition may then be removed from the reactor by purging and/or evacuating the reactor.
- a co-reactant for example, O 3
- Any excess co-reactant is removed from the reactor by purging and/or evacuating the reactor. If the desired film is a Group V-containing oxide, this two-step process may provide the desired film thickness may be repeated until a film having the necessary thickness has been obtained.
- the two-step process above may be followed by introduction of the vapor of an additional precursor compound into the reactor.
- the additional precursor compound will be selected based on the nature of the Group V-containing film being deposited.
- the additional precursor compound is contacted with the substrate. Any excess precursor compound is removed from the reactor by purging and/or evacuating the reactor.
- a co-reactant may be introduced into the reactor to react with the precursor compound. Excess co-reactant is removed from the reactor by purging and/or evacuating the reactor. If a desired film thickness has been achieved, the process may be terminated.
- the entire four-step process may be repeated.
- a film of desired composition and thickness can be deposited.
- a co-reactant for example, O 3
- O 3 co-reactant
- Any excess O 3 gas is removed from the reactor by purging and/or evacuating the reactor.
- a Li- containing precursor may then be exposed to the powder substrate and/or the Nb oxide film to form a Li and Nb oxide film LiNbO 3 .
- LiOtBu may serve as the Li precursor.
- the resulting LINbOs film may be used in rechargeable battery applications.
- the suitable lithium precursors include, but are not limited to, LiOtBu, LiN(Si R 3 ) 2 wherein each R is selected from H, a C 1 to C4 alkyl or alkeny group, Li(DPM) (lithium dipivaloylmethane aka lithium 2, 2,6,6- tetramethyl-3,5-heptanedionate) or any other suitable lithium ALD precursors.
- the exemplary ALD process becomes an exemplary PEALD process.
- the co-reactant may be treated with plasma prior subsequent to introduction into the chamber.
- a co-reactant for example, O 3
- any excess O 3 gas is removed from the reactor by purging and/or evacuating the reactor. These two steps may be repeated until the Group V-containing oxide film obtains a desired thickness, typically around 10 angstroms, ZrO 2 may then be deposited on the Group V-containing oxide film, For example, ZrCp(NMe 2 ) 3 or HfCp(NMe 2 ) 3 may serve as the Zr or Hf precursor repectively.
- the resultingNb 2 O 5 /ZrO 2 /Nb 2 O 5 , Nb 2 O 5 /HfO 2 /Nb 2 O 5 or Nb 2 O 5 /HZO/Nb 2 O 5 stack may be used in DRAM capacitors.
- HZO represents Hafnium Zirconium Oxide.
- another precursor may be introduced sequentially between one several ALD super-cycles (e.g., O-containing co-reactant/ Group V-containing precursor/O-containing co-reactant) in order to deposit a Group V-containing MO film an Group V (five)-containing O/MO nanolaminate, M being selected from a Group IV element a different group V (five) element, silicon, germanium, aluminium, or any lanthanide.
- the M precursor selected preferably undergoes ALD growth in the same temperature window exhibited by the selected Group V-containing film forming composition.
- the Group V-containing films resulting from the processes discussed above may include Nb, NbkSii, Nb n O m , Nb 0 N p , Nb o N p O q , wherein k, I, m, n, 0, p, and q may each independently range from 1 to 6.
- Exemplary films include NbO 2 , Nb 2 O 5 , NbN, and NbON,
- the Group V-containing films may provide suitable step coverage for capacitor electrodes in DRAM, the gate metal in 3D Flash memory devices, the heating element in phase change memory, the electromigration barrier layer, gate metal, and contact layers in logic devices.
- the film may be subject to further processing, such as thermal annealing, furnace-annealing, rapid thermal annealing, UV e- beam curing, and microwave annealing and/or plasma gas exposure.
- further processing such as thermal annealing, furnace-annealing, rapid thermal annealing, UV e- beam curing, and microwave annealing and/or plasma gas exposure.
- the Nb 2 O 5 film may be exposed to a temperature ranging from approximately 200°C and approximately 1000°C for a time ranging from approximately 0.1 second to approximately 7200 seconds under an inert atmosphere, an O-containing atmosphere, H ⁇ containing atmosphere combinations thereof. Most preferably, the temperature is 400°C for 3600 seconds under an inert atmosphere or an O-containing atmosphere.
- the resulting film may contain fewer impurities and therefore may have an improved density resulting in improved leakage current.
- the annealing step may be performed in the same reaction chamber in which the deposition process is performed. Alternatively, the substrate may be removed from the reaction chamber, with the annealing/flash annealing process being performed in a separate apparatus. Any of the above post-treatment methods, but especially thermal annealing, has been found effective to reduce carbon and nitrogen contamination of the Nb 2 O 5 film. This in turn tends to improve the resistivity of the film.
- the Group V-containing films deposited by any of the disclosed processes may have a bulk resistivity at room temperature of approximately 50 pohm-cm to approximately 1 ,000 pohm-cm. Room temperature is approximately 20°C to approximately 28°C depending on the season. Bulk resistivity is also known as volume resistivity.
- the bulk resistivity is measured at room temperature on the Group V-containing films that are typically approximately 50 nm thick. The bulk resistivity typically increases for thinner films due to changes in the electron transport mechanism. The bulk resistivity also increases at higher temperatures.
- the disclosed compositions may be used as doping implantation agents.
- Part of the disclosed Group V-containing film forming composition may be deposited on top of the film to be doped, such as an indium oxide (ln 2 O 3 ) film, tantalum dioxide (TaO 2 ), vanadium dioxide (VO 2 ) film, a titanium oxide film, a copper oxide film, or a tin dioxide (SnO 2 ) film.
- the Group V (five) element for example Nb
- the Group V (five) element then diffuses into the film during an annealing step to form the Group V (five) element-doped films, such as ⁇ (Nb)ln 2 O 3 , (Nb)VO 2 , (Nb)TiO, (Nb)CuO, (Nb)SnO 2 ⁇ .
- the Group V (five) element-doped films such as ⁇ (Nb)ln 2 O 3 , (Nb)VO 2 , (Nb)TiO, (Nb)CuO, (Nb)SnO 2 ⁇ .
- the purified product left a 1.2% residual mass during open-cup TGA analysis measured at a temperature rising rate of 10'C/min in an inert atmosphere that flows nitrogen at 200 mL/min.
- the results are shown in FIG. 1, which is a TGA graph illustrating the percentage of weight loss upon temperature increase.
- Onset temperature of melting (26°C) and decomposition (422“C) of the product were measured by differential scanning calorimetry (DSC), which are shown in FIG. 2.
- O 3 was used as oxygen source.
- the substrate was heated from 200 to 400°C.
- An Ar purge of 10s was performed afterwards as second step.
- a pulse of O 3 was then introduced into the reaction chamber in 1s, an Nb 2 O 5 fiim. Self-limited atomic layer deposition was obtained.
- the growth rate was 0.3A per cycle and the ALD window was up to 325°C (FIG. 3).
- FIG. 4a showed a full image of excellent step coverage in 1 :15 aspect ratio patterned wafer at 325°C by SEM.
- FIG, 4b showed top image of FIG. 4a and FIG. 4c showed bottom image of FIG. 4a.
- FIG. 5 is an XPS depth profile that shows proper composition ratio of Nb 2 O 5 and negligible Impurity level at 325°C.
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Abstract
Methods for forming a Group V-containing film comprise: a) exposing a substrate to a vapor of a Group V (five)-containing film forming composition; b) exposing the substrate to a co-reactant; and C) repeating the steps of a) and b) until a desired thickness of the Group V (five)-containing film is deposited on the substrate using a vapor deposition process, wherein the Group V (five)-containing film forming composition comprises a precursor having the formula: (Formula should be inserted here) wherein M is Group V (five) element, vanadium (V), niobium (Nb), or tantalum (Ta); R1 to R8 each is H, a C1-C6 alkyl group, a fluoro group, an alkylsilyl group, a germyl group, an alkylamide or an alkylsilylamide; m = 1 to 5, n = 1 to 5.
Description
NIOBIUM, VANADIUM, TANTALUM FILM FORMING COMPOSITIONS AND DEPOSITION OF GROUP V (FIVE) CONTAINING FILMS USING THE SAME
Technical Field
[0001] The present invention relates to Group V (five)-containing film forming compositions, methods of synthesizing the same, and methods of using the same to deposit Group V-containing films on substrates via vapor deposition processes. The Group V- containing film forming composition comprises a precursor having the formula:
wherein M is Group V (five) element, vanadium (V), niobium (Nb), or tantalum (Ta);
R1 to R8 each Is H, a C1-C6 alkyl group, a fluoro group, an alkylsilyl group, a germyl group, an alkylamide or an alkylsilylamide; m = 1 to 5, n = 1 to 5.
Background
[0002] Today, the needs for metal organic precursors in liquid state at room temperature or close to room temperature, whcih have high volatility, thermal stability and high versatility, and suitable for various applications in the semiconductor manufacture, still exist. Interest for conductive (resistivity 1000 pQ.cm), Group V (five) (V, Nb, Ta) metal containing thin films deposited by atomic layer deposition (ALD) has risen in the past few years for several main applications such as: copper diffusion barrier in back end of line (BEOL) applications, complementary metal-oxide-semiconductor (CMOS) metal gate, electrodes for Metal- Insulator-Metal applications (DRAM, etc.), and the thin film transistor liquid crystal display (TFT -LCD) applications. Group V (five) (V, Nb, Ta) metal containing films are also of particular interest for high-k layers in memory devices.
[0003] Halides, such as CpNbCl4 (CAS 33114-1507), NbF5, NbBr5 (Thin solid films, 1981 , 79, 75), NbCI5 (Crystal growth, 1978, 45, 37) and TaCI5 (US 6,268,288), have been widely investigated. However, some by-products generated during the deposition process, such as HCI or CI2, cause surface/interface roughness that can be detrimental to the final films.
Moreover, Cl or F impurities are detrimental to the final electrical properties. It is therefore expected to find new compounds having sufficient volatility but without containing Cl, F, or Br atoms.
[0004] Many Group V (five) precursors have been considered to enable such deposition. Examples include: Alkoxides such as penta-ethoxy-tantalum (PET) are widely used and disclosed. However, they lead to oxygen containing films and are not suitable for the deposition of metal containing films which are used in particular as electrodes and which should not contain oxygen even at trace levels. The same problem is observed for compounds such as Cp2Nb(H)(CO), CpNb(CO)4 (J. Organomet. Chem., 557 (1998) 77-92), V(CO)6 (Thermochimica Acta, 1984, 75, 71), (η5 -C5H5)V(CO)4 (M. L. Green, R. A. Levy, J. Metals 37 (1985) 63).
[000S] US 6,379,748 discloses an improvement to Ta(OEt)5 (PET). Alkyl bonds have been introduced, e.g. by using TaMe3(OEt)2 instead of Ta(OEt)5 (PET). Volatility was thereby significantly improved without affecting the melting point. However, TaMe3(OEt)2 does not allow versatile deposition: in particular, oxygen free metal cannot be obtained.
[0006] US 6,368,398 discloses another improvement with the use for instance of Ta[OC(O)C(CH3)3]5, however with the same limitation as disclosed here above.
[0007] WO 2002/20870 discloses the deposition of Ta2O5 use using tert- butylimido(tris(diethylamido)tantalum (TBTDET).
[0008] US 6,593,484 and US 2004/0219784 disclose a method of deposition of tantalum nitride films by sequential injection of TBTDET or tertiary amyl imido-tris-dimethylamido tantalum (Ta(NC(CH3)2C2H5)(N(CH3)2)3 (TAI MATA) and other N source.
[0009] US 6,379,748 discloses Ta(Me3SiCp)2H3, which is a biscyclopentadienyl Ta hydride and is a solid having a low volatility.
[0010] US 8,460,989 discloses a method of deposition of Niobium-containing films by CVD and ALD of NbCp(=NtBu)(NEtMe)2.
Summary
[0011] Disclosed is a method for forming a Group V (five)-containing film, the method comprising the steps of: a) exposing a substrate to a vapor of a Group V (five)-containing film forming composition; b) exposing the substrate to a co-reactant; and c) repeating the steps of a) and b) until a desired thickness of the Group V (five)- containing film is deposited on the substrate using a vapor deposition process,
wherein the Group V (five)-containing film forming composition comprises a precursor having the formula:
wherein M is Group V (five) element, vanadium (V), niobium (Nb), or tantalum (Ta);
R1 to R8 each is H, a C1-C6 alkyl group, a fluoro group, an alkylsilyl group, a germyl group, an alkylamide or an alkylsilylamide; m = 1 to 5, n = 1 to 5. The disclosed methods may include one or more of the following aspects:
« further comprising the steps of introducing an inert gas purge following the steps a) and b), respectively, to separate each exposure;
» the inert gas purge using an inert gas selected from N2, He, Ar, Kr, or Xe;
* the inert gas purge using Ar;
* further comprising the step of plasma treating the co-reactant;
* the co-reactant being selected from the group consisting of O2, O3, H2O, H2O2, NO, N2O, NO2, oxygen radicals thereof, and mixtures thereof;
* the co-reactant being O3;
* the co-reactant being selected from the group consisting of H2, H2CO, N2H4, NH3, an amine, a hydrazine N(SiH3)3, B2H6, Si2Hs radicals thereof, and mixtures thereof;
* the co-reactant being NH3 or O3;
* the precursor being Niobium tButyl Imido Cyclopentadienyl tAmyl-Diazadienyl, CpNb(=NtBu)(tAm2-DAD);
* the precursor being (R3'7Cp)Nb(=NR1)(R2 2-DAD),
wherein DAD = Diazadiene; R1 is tBu or nPr ; R2 is Me, Et, nPr, IPr, nBu, tBu, nPentyl or tAm;
R3, R4, R5, R6 and R7 each is Independently H, Me, Et, nPr, iPr, nBu, tBu or sBu;
» (R3'7Cp)Nb(=NR1)(R22-DAD) including (Cp)Nb(=NtBu)(Me2-DAD)1
(Cp)Nb(=NtBu)(Et2-DAD), (Cp)Nb(=NtBu)(nPr2-DAD), (Cp)Nb(=NtBu)(iPr2-DAD),
(Cp)Nb(=NtBu)(nBu2-DAD), (Cp)Nb(=NtBu)(tBu2~DAD), (Cp)Nb(=NtBu)(nPentyi2-DAD),
(Cp)Nb(=NtBu)(tAm2-DAD), (MeCp)Nb(=NtBu)(Me2-DAD), (MeCp)Nb(=NtBu)(Et2-DAD),
(MeCp)Nb(=NtBu)(nPr2-DAD), (MeCp)Nb(=NtBu)(iPr2-DAD), (MeCp)Nb(=NtBu)(nBu2- DAD), (MeCp)Nb(=NtBu)(tBu2”DAD), (MeCp)Nb(=NtBu)(nPentyl2~DAD),
(MeCp)Nb(=NtBu)(tAm2-DAD), (EtCp)Nb(=NtBu)(Me2-DAD), (EtCp)Nb(=NtBu)(Et2-DAD),
(EtCp)Nb(=NtBu)(nPr2-DAD), (EtCp)Nb(=NtBu)(iPr2-DAD), (EtCp)Nb(=NtBu)(nBu2-DAD),
(EtCp)Nb(~NtBu)(tBu2-DAD), (EtCp)Nb(=NtBu)(nPentyi2-DAD), (EtCp)Nb(=NtBu)(tAm2-
DAD), (nPrCp)Nb(=NtBu)(Me2-DAD), (nPrCp)Nb(=NtBu)(Et2-DAD),
(nPrCp)Nb(=NtBu)(nPr2-DAD), (nPrCp)Nb(=NtBu)(iPr2-DAD), (nPrCp)Nb(=NtBu)(nBu2-
DAD), (nPrCp)Nb(=NtBu)(tBu2-DAD), (nPrCp)Nb(=NtBu)(nPentyl2~DAD),
(nPrCp)Nb(=NtBu)(tAm2-DAD), (iPrCp)Nb(=NtBu)(Me2-DAD), (iPrCp)Nb(=NtBu)(Et2-DAD),
(iPrCp)Nb(=NtBu)(nPr2-DAD), (iPrCp)Nb(=NtBu)(iPr2-DAD), (iPrCp)Nb(=NtBu)(nBu2-DAD),
(iPrCp)Nb(=NtBu)(tBu2-DAD), (iPrCp)Nb(=NtBu)(nPentyl2-DAD), (iPrCp)Nb(=NtBu)(tAm2-
DAD), (nBuCp)Nb(=NtBu)(Me2-DAD), (nBuCp)Nb(=NtBu)(Et2-DAD),
(nBuCp)Nb(=NtBu)(nPr2-DAD), (nBuCp)Nb(=NtBu)(iPr2-DAD), (nBuCp)Nb(=NtBu)(nBu2-
DAD), (nBuCp)Nb(=NtBu)(tBu2-DAD), (nBuCp)Nb(=NtBu)(nPentyl2-DAD)(
(nBuCp)Nb(=NtBu)(tAm2-DAD), (tBuCp)Nb(=NtBu)(Me2-DAD)1 (tBuCp)Nb(=NtBu)(Et2-
DAD), (tBuCp)Nb(=NtBu)(nPr2~DAD), (tBuCp)Nb(=NtBu)(iPr2-DAD),
(tBuCp)Nb(=NtBu)(nBu2-DAD), (tBuCp)Nb(=NtBu)(tBu2-DAD), (tBuCp)Nb(=NtBu)(nPentyi2-
DAD), (tBuCp)Nb(=NtBu)(tAm2-DAD), (sBuCp)Nb(=NtBu)(Me2-DAD),
(sBuCp)Nb(=NtBu)(Et2-DAD), (sBuCp)Nb(=NtBu)(nPr2-DAD), (sBuCp)Nb(=NtBu)(iPr2-
DAD), (sBuCp)Nb(=NtBu)(nBu2-DAD), (sBuCp)Nb(=NtBu)(tBu2-DAD),
(sBuCp)Nb(=NtBu)(nPentyl2-DAD), (sBuCp)Nb(=;NtBu)(tAm2-DAD), (Di-
MeCp)Nb(=NtBu)(Me2-DAD), (Di-MeCp)Nb(=NtBu)(Et2-DAD), (Di-MeCp)Nb(=NtBu)(nPr2-
DAD), (Di-MeCp)Nb(=NtBu)(!Pr2-DAD), (Di-MeCp)Nb(=NtBu)(nBu2-DAD), (Di-
MeCp)Nb(=NtBu)(tBu2-DAD), (Di-MeCp)Nb(=NtBu)(nPentyi2-DAD), (Di-
MeCp)Nb(=NtBu)(tAm2-DAD), (MeEtCp)Nb(=NtBu)(Me2-DAD), (MeEtCp)Nb(=NtBu)(Et2~ DAD), (MeEtCp)Nb(=NtBu)(nPr2-DAD), (MeEtCp)Nb(=NtBu)(iPr2-DAD), (MeEtCp)Nb(=NtBu)(nBu2-DAD), (MeEtCp)Nb(=NtBu)(tBu2-DAD)i
(MeEtCp)Nb(=NtBu)(nPentyl2-DAD), (MeEtCp)Nb(~NtBu)(tAm2-DAD),
(MePrCp)Nb(=NtBu)(Me2-DAD), (MePrCp)Nb(=NtBu)(Et2-DAD), (MePrCp)Nb(=NtBu)(nPr2- DAD), (MePrCp)Nb(=NtBu)(iPr2-DAD), (MePrCp)Nb(=NtBu)(nBu2-DAD)i
(MePrCp)Nb(=NtBu)(tBu2~DAD), (MePrCp)Nb(=NtBu)(nPentyl2-DAD),
(MePrCp)Nb(=NtBu)(tAm2-DAD), (Penta-MeCp)Nb(=NtBu)(Me2-DAD), (Penta-
MeCp)Nb(=NtBu)(Et2-DAD), (Penta-MeCp)Nb(=NtBu)(nPr2-DAD), (Penta-
MeCp)Nb(=NtBu)(iPr2-DAD), (Penta-MeCp)Nb(=NtBu)(nBu2-DAD), (Penta-
MeCp)Nb(=NtBu)(tBu2-DAD), (Penta-MeCp)Nb(=NtBu)(nPentyl2-DAD), (Penta-
MeCp)Nb(=NtBu)(tAm2-DAD), (Cp)Nb(=NnPr)(Me2-DAD), (Cp)Nb(=NnPr)(Et2-DAD),
(Cp)Nb(=NnPr)(nPr2-DAD), (Cp)Nb(=NnPr)(iPr2-DAD), (Cp)Nb(=NnPr)(nBu2-DAD),
(Cp)Nb(=NnPr)(tBu2-DAD), (Cp)Nb(=NnPr)(nPentyE-DAD): (Cp)Nb(=NnPr)(tAm2-DAD),
(MeCp)Nb(=NnPr)(Me2-DAD), (MeCp)Nb(=NnPr)(Et2-DAD), (MeCp)Nb(=NnPr)(nPr2-DAD),
(MeCp)Nb(=NnPr)(iPr2-DAD), (MeCp)Nb(=NnPr)(nBu2-DAD), (MeCp)Nb(=NnPr)(tBu2-
DAD), (MeCp)Nb(=NnRr)(nPentyl2-DAD), (MeCp)Nb(=NnPr)(tAm2-DAD),
(EtCp)Nb(=NnPr)(Me2-DAD), (EtCp)Nb(=NnPr)(Et2-DAD), (EtCp)Nb(=NnPr)(nPr2-DAD),
(EtCp)Nb(=NnPr)(iPr2-DAD), (EtCp)Nb(~NnPr)(nBu2-DAD), (EtCp)Nb(=NnPr)(tBu2-DAD),
(EtCp)Nb(=NnPr)(nPentyl2-DAD), (EtCp)Nb(=NnPr)(tAm2-DAD)! (nPrCp)Nb(=NnPr)(Me2-
DAD), (nPrCp)Nb(=NnPr)(Et2-DAD), (nPrCp)Nb(=NnPr)(nPr2-DAD),
(nPrCp)Nb(=NnPr)(iPr2-DAD), (nPrCp)Nb(=NnPr)(nBu2-DAD), (nPrCp)Nb(=NnPr)(tBu2-
DAD), (nPrCp)Nb(=NnPr)(nPentyl2-DAD), (nPrCp)Nb(=NnPr)(tAm2-DAD),
(iPrCp)Nb(=NnPr)(Me2-DAD), (iPrCp)Nb(=NnPr)(Et2-DAD), (iPrCp)Nb(=NnPr)(nPr2-DAD)i
(iPrCp)Nb(=NnPr)(iPr2-DAD), (iPrCp)Nb(=NnPr)(nBu2-DAD), (iPrCp)Nb(~NnPr)(tBu2~DAD),
(iPrCp)Nb(=NnPr)(nPentyl2-DAD), (iPrCp)Nb(=NnPr)(tAm2-DAD), (nBuCp)Nb(=NnPr)(Me2- DAD), (nBuCp)Nb(=NnPr)(Et2-DAD), (nBuCp)Nb(=NnPr)(nPr2-DAD),
(nBuCp)Nb(=NnPr)(iPr2-DAD), (nBuCp)Nb(~NnPr)(nBu2~DAD), (nBuCp)Nb(=NnPr)(tBu2-
DAD), (nBuCp)Nb(=NnPr)(nPentyi2-DAD), (nBuCp)Nb(=NnPr)(tAm2-DAD),
(tBuCp)Nb(=NnPr)(Me2-DAD), (tBuCp)Nb(=NnPr)(Et2-DAD): (tBuCp)Nb(=NnPr)(nPr2-DAD),
(tBuCp)Nb(=NnPr)(iPr2-DAD), (tBuCp)Nb(=NnPr)(nBu2-DAD), (tBuCp)Nb(=NnPr)(tBu2-
DAD), (tBuCp)Nb(=NnPr)(nPenty!2-DAD), (tBuCp)Nb(=NnPr)(tAm2-DAD)s
(sBuCp)Nb(=NnPr)(Me2-DAD), (sBuCp)Nb(=NnPr)(Et2-DAD), (sBuCp)Nb(=NnPr)(nPr2-
DAD), (sBuCp)Nb(=NnPr)(iPr2-DAD), (sBuCp)Nb(=NnPr)(nBu2-DAD),
(sBuCp)Nb(=NnPr)(tBu2-DAD), (sBuCp)Nb(=NnPr)(nPentyl2-DAD),
(sBuCp)Nb(=NnPr)(tAm2-DAD), (Di-MeCp)Nb(=NnPr)(Me2-DAD), (Di-
MeCp)Nb(=NnPr)(Et2-DAD), (Di-MeCp)Nb(=NnPr)(nPr2-DAD), (Di-MeCp)Nb(=NnPr)(iPr2-
DAD), (Di-MeCp)Nb(=NnPr)(nBu2-DAD), (Di-MeCp)Nb(=NnPr)(tBu2-DAD)s (Di-
MeCp)Nb(=NnPr)(nPentyl2-DAD), (Di-MeCp)Nb(=NnPr)(tAm2-DAD)i
(MeEtCp)Nb(=NnPr)(Me2-DAD), (MeEtCp)Nb(=NnPr)(Et2-DAD), (MeEtCp)Nb(=NnPr)(nPr2- DAD), (MeEtCp)Nb(=NnPr)(iPr2-DAD), (MeEtCp)Nb(=NnPr)(nBu2-DAD),
(MeEtCp)Nb(=NnPr)(tBu2-DAD), (MeEtCp)Nb(=NnPr)(nPentyl2-DAD),
(MeEtCp)Nb(=NnPr)(tAm2-DAD), (MePrCp)Nb(~NnPr)(Me2-DAD), (MePrCp)Nb(=NnPr)(Et2-DAD), (MePrCp)Nb(=NnPr)(nPr2-DAD), (MePrCp)Nb(=NnPr)(iPr2- DAD), (MePrCp)Nb(=NnPr)(nBu2-DAD), (MePrCp)Nb(= NnPr)(tBu2-DAD), (MePrCp)Nb(=NnPr)(nPentyl2-DAD), (MePrCp)Nb(=NnPr)(tAm2-DAD), (Penta- MeCp)Nb(=NnPr)(Me2-DAD), (Penta-MeCp)Nb(=NnPr)(Et2-DAD), (Penta- MeCp)Nb(=NnPr)(nPr2-DAD), (Penta.-MeCp)Nb(-NnPr)(iPr2-DAD). (Penta- MeCp)Nb(=NnPr)(nBu2-DAD), (Penta-MeCp)Nb(=NnPr)(tBu2-DAD), (Penta- MeCp)Nb(=NnPr)(nPentyl2-DAD), or (Penta-MeCp)Nb(=NnPr)(tAm2-DAD).
® The precursor being (R3’7Cp)Nb(=NR1)(R2 2~EDA),
wherein EDA is Ethylenediamine; R1 is tBu or nPr ; R2 is Me, Et, nPr, iPr, nBu, tBu, nPentyl or tAm; R3, R4, R5, R6 and R7 each is independently H, Me, Et, nPr, iPr, nBu, tBu or sBu;
• (R3'7Cp)Nb(=NR1 >(RVEDA) including (Cp)Nb(=NtBu)(EDA), (Cp)Nb(==NtBu)(Me2- EDA), (Cp)Nb(=NtBu)(Et2-EDA), (Cp)Nb(=NtBu)(nPr2-EDA), (Cp)Nb(=NtBu)(iPr2-EDA), (Cp)Nb(=NtBu)(nBu2-EDA), (Cp)Nb(=NtBu)(tBu2-EDA), (Cp)Nb(=NtBu)(nPentyl2-EDA), (Cp)Nb(=NtBu)(tAm2-EDA), (MeCp)Nb(=NtBu)(EDA), (MeCp)Nb(=NtBu)(Me2-EDA), (MeCp)Nb(=NtBu)(Et2-EDA), (MeCp)Nb(=NtBu)(nPr2-EDA), (MeCp)Nb(=NtBu)(iPr2-EDA), (MeCp)Nb(=NtBu)(nBu2-EDA), (MeCp)Nb(=NtBu)(tBu2-EDA), (MeCp)Nb(=NtBu)(nPentyl2- EDA), (MeCp)Nb(=NtBu)(tAm2-EDA), (EtCp)Nb(=NtBu)(EDA), (EtCp)Nb(=NtBu)(Me2-EDA), (EtCp)Nb(=NtBu)(Et2-EDA), (EtCp)Nb(=NtBu)(nPr2-EDA), (EtCp)Nb(=NtBu)(iPr2-EDA), (EtCp)Nb(=NtBu)(nBu2-EDA), (EtCp)Nb(=NtBu)(tBu2-EDA), (EtCp)Nb(=NtBu)(nPentyl2- EDA), (EtCp)Nb(=NtBu)(tAm2-EDA), (nPrCp)Nb(=NtBu)(EDA), (nPrCp)Nb(=NtBu)(Me2- EDA), (nPrCp)Nb(=NtBu)(Et2-EDA), (nPrCp)Nb(=NtBu)(nPr2-EDA), (nPrCp)Nb(=NtBu)(IPr2- EDA), (nPrCp)Nb(=NtBu)(nBu2-EDA), (nPrCp)Nb(=NtBu)(tBu2-EDA), (nPrCp)Nb(=NtBu)(nPenty!2-EDA), (nPrCp)Nb(=NtBu)(tAm2-EDA), (IPrCp)Nb(=NtBu)(EDA), (iPrCp)Nb(=NtBu)(Me2-EDA), (iPrCp)Nb(=NtBu)(Et2-EDA), (iPrCp)Nb(=NtBu)(nPr2~EDA), (iPrCp)Nb(=NtBu)(iPr2-EDA), (iPrCp)Nb(=NtBu)(nBu2-EDA), (iPrCp)Nb(=NtBu)(tBu2-EDA), (iPrCp)Nb(=NtBu)(nPenty!2-EDA), (iPrCp)Nb(=NtBu)(tAm2-EDA), (nBuCp)Nb(=NtBu)(EDA), (nBuCp)Nb(=NtBu)(Me2-EDA), (nBuCp)Nb(=NtBu)(Et2-EDA), (nBuCp)Nb(=NtBu)(nPr2- EDA), (nBuCp)Nb(=NtBu)(iPr2-EDA), (nBuCp)Nb(=NtBu)(nBu2-EDA),
(nBuCp)Nb(=NtBu)(tBu2-EDA), (nBuCp)Nb(=NtBu)(nPentyh-EDA),
(nBuCp)Nb(=NtBu)(tAm2-EDA), (tBuCp)Nb(=NtBu)(EDA), (tBuCp)Nb(=NtBu)(Me2-EDA)i
(tBuCp)Nb(=NtBu)(Et2-EDA)i (tBuCp)Nb(=NtBu)(nPr2-EDA), (tBuCp)Nb(=:NtBu)(iPi‘2-EDA), (tBuCp)Nb(=NtBu)(nBu2-EDA)1 (tBuCp)Nb(=NtBu)(tBu2-EDA), (tBuCp)Nb(=NtBu)(nPentyl2- EDA), (tBuCp)Nb(=NtBu)(tAm2-EDA)! (sBuCp)Nb(=NtBu)(EDA), (sBuCp)Nb(=NtBu)(Me2- EDA), (sBuCp)Nb(=NtBu)(Et2-EDA), (sBuCp)Nb(=NtBu)(nPr2-EDA),
(sBuCp)Nb(=NtBu)(iPr2-EDA), (sBuCp)Nb(=NtBu)(nBu2-EDA), (sBuCp)Nb(=NtBu)(tBu2- EDA), (sBuCp)Nb(=NtBu)(nPentyi2-EDA), (sBuCp)Nb(=NtBu)(tAm2-EDA), (Di- MeCp)Nb(=NtBu)(EDA), (Di-MeCp)Nb(=NtBu)(Me2-EDA), (Di-MeCp)Nb(=NtBu)(Et2-EDA), (Di-MeCp)Nb(=NtBu)(nPr2-EDA), (Di-MeCp)Nb(=NtBu)(iPr2-EDA), (Di-
MeCp)Nb(=NtBu)(nBu2-EDA), (Di-MeCp)Nb(=NtBu)(tBu2-EDA), (Di-
MeCp)Nb(=NtBu)(nPentyl2~EDA)> (Di-MeCp)Nb(~NtBu)(tAm2-EDA),
(MeEtCp)Nb(=NtBu)(EDA), (MeEtCp)Nb(=NtBu)(Me2-EDA), (MeEtCp)Nb(=NtBu)(Et2-EDA),
(MeEtCp)Nb(=NtBu)(nPr2-EDA), (MeEtCp)Nb(=NtBu)(iPr2-EDA),
(MeEtCp)Nb(=NtBu)(nBu2-EDA), (MeEtCp)Nb(=NtBu)(tBu2"EDA),
(MeEtCp)Nb(=NtBu)(nPentyi2-EDA), (MeEtCp)Nb(=NtBu)(tAm2-EDA),
(MePrCp)Nb(=NtBu)(EDA), (MePrCp)Nb(=NtBu)(Me2-EDA), (MePrCp)Nb(= NtBu)(Et2- EDA), (MePrCp)Nb(=NtBu)(nPr2-EDA), (MePrCp)Nb(=NtBu)(iPr2-EDA),
(MePrCp)Nb(=NtBu)(nBu2-EDA), (MePrCp)Nb(=NtBu)(tBu2-EDA),
(MePrCp)Nb(=NtBu)(nPentyl2"EDA)1 (MePrCp)Nb(=NtBu)(tAm2-EDA), (Penta-
MeCp)Nb(=NtBu)(EDA), (Penta~MeCp)Nb(=NtBu)(Me2~EDA)! (Penta~MeCp)Nb(~NtBu)(Et2- EDA), (Penta-MeCp)Nb(=NtBu)(nPr2-EDA), (Penta-MeCp)Nb(=NtBu)(iPr2-EDA), (Penta- MeCp)Nb(=NtBu)(nBu2“EDA), (Penta-MeCp)Nb(=NtBu)(tBu2- EDA). (Penta-
MeCp)Nb(=NtBu)(nPentyl2~EDA), (Penta-MeCp)Nb(~NtBu)(tAm2-EDA),
(Cp)Nb(=NnPr)(EDA), (Cp)Nb(=NnPr)(Me2-EDA)s (Cp)Nb(=NnPr)(Et2-EDA),
(Cp)Nb(=NnPr)(nPr2-EDA), (Cp)Nb(=NnPr)(iPr2-EDA): (Cp)Nb(=NnPr)(nBu2-EDA),
(Cp)Nb(=NnPr)(tBu2-EDA), (Cp)Nb(=NnPr)(nPentyi2-EDA), (Cp)Nb(=NnPr)(tAm2-EDA),
(MeCp)Nb(=NnPr)(EDA), (MeCp)Nb(=NnPr)(Me2-EDA), (MeCp)Nb(=NnPr)(Et2-EDA), (MeCp)Nb(=NnPr)(nPr2-EDA), (MeCp)Nb(=NnPr)(iPr2-EDA), (MeCp)Nb(=NnPr)(nBu2- EDA): (MeCp)Nb(=NnPr)(tBu2-EDA), (MeCp)Nb(=NnPr)(nPenty!2-EDA),
(MeCp)Nb(=NnPr)(tAm2-EDA), (EtCp)Nb(=NnPr)(EDA), (EtCp)Nb(=NnPr)(Me2-EDA),
(EtCp)Nb(=NnPr)(Et2-EDA), (EtCp)Nb(=NnPr)(nPr2-EDA), (EtCp)Nb(=NnPr)(iPr2-EDA), (EtCp)Nb(=NnPr)(nBu2-EDA), (EtCp)Nb(=NnPr)(tBu2-EDA), (EtCp)Nb(=NnPr)(nPentyl2- EDA), (EtCp)Nb(=NnPr)(tAm2-EDA), (nPrCp)Nb(=NnPr)(EDA), (nPrCp)Nb(=NnPr)(Me2- EDA), (nPrCp)Nb(=NnPr)(Et2~EDA), (nPrCp)Nb(=NnPr)(nPr2-EDA),
(nPrCp)Nb(=NnPr)(iPr2-EDA), (nPrCp)Nb(=NnPr)(nBu2-EDA), (nPrCp)Nb(=NnPr)(tBu2- EDA), (nPrCp)Nb(=NnPr)(nPentyl2-EDA), (nPrCp)Nb(=NnPr)(tAm2-EDA), (iPrCp)Nb(=NnPr)(EDA), (iPrCp)Nb(=NnPr)(Me2-EDA), (iPrCp)Nb(=NnPr)(Et2-EDA), (jPrCp)Nb(=NnPr)(nPr2-EDA), (iPrCp)Nb(=NnPr)(iPr2-EDA), (iPrCp)Nb(=NnPr)(nBu2-EDA), (iPrCp)Nb(=NnPr)(tBu2-EDA), (iPrCp)Nb(=NnPr)(nPentyl2-EDA)! (iPrCp)Nb(=NnPr)(tAm2- EDA), (nBuCp)Nb(=NnPr)(EDA), (nBuCp)Nb(=NnPr)(Me2-EDA)! (nBuCp)Nb(=NnPr)(Et2- EDA), (nBuCp)Nb(=NnPr)(nPr2~EDA), (nBuCp)Nb(=NnPr)(iPr2-EDA),
(nBuCp)Nb(=NnPr)(nBu2-EDA), (nBuCp)Nb(=NnPr)(tBu2-EDA), (nBuCp)Nb(=NnPr)(nPentyl2-EDA), (nBuCp)Nb(=NnPr)(tAm2-EDA), (tBuCp)Nb(=NnPr)(EDA), (tBuCp)Nb(=NnPr)(Me2-EDA), (tBuCp)Nb(=NnPr)(Et2-EDA), (tBuCp)Nb(=NnPr)(nPr2-EDA), (tBuCp)Nb(=NnPr)(iPr2-EDA), (tBuCp)Nb(=NnPr)(nBu2- EDA), (tBuCp)Nb(=NnPr)(tBu2-EDA), (tBuCp)Nb(=NnPr)(nPentyl2-EDA), (tBuCp)Nb(=NnPr)(tAm2-EDA), (sBuCp)Nb(=NnPr)(EDA), (sBuCp)Nb(=NnPr)(Me2-EDA), (sBuCp)Nb(=NnPr)(Et2-EDA), (sBuCp)Nb(=NnPr)(nPr2-EDA), (sBuCp)Nb(=NnPr)(iPr2- EDA), (sBuCp)Nb(=NnPr)(nBu2-EDA), (sBuCp)Nb(~NnPr)(tBu2-EDA),
(sBuCp)Nb(=NnPr)(nPentyh-EDA), (sBuCp)Nb(=NnPr)(tAm2-EDA), (Di- MeCp)Nb(=NnPr)(EDA), (Di-MeCp)Nb(=NnPr)(Me2-EDA), (Di-MeCp)Nb(=NnPr)(Et2~EDA), (Di-MeCp)Nb(=NnPr)(nPr2-EDA), (Di-MeCp)Nb(=NnPr)(iPr2-EDA), (Di~ MeCp)Nb(=NnPr)(nBu2-EDA), (Di-MeCp)Nb(=NnPr)(tBu2-EDA), (Di- MeCp)Nb(=NnPr)(nPentyl2-EDA), (Di-MeCp)Nb(=NnPr)(tAm2-EDA), (MeEtCp)Nb(=NnPr)(EDA), (MeEtCp)Nb(=NnPr)(Me2-EDA), (MeEtCp)Nb(=NnPr)(Et2~ EDA), (MeEtCp)Nb(=:NnPr)(nPr2-EDA): (MeEtCp)Nb(=NnPr)(iPr2-EDA),
(MeEtCp)Nb(=NnPr)(nBu2-EDA), (MeEtCp)Nb(=NnPr)(tBu2-EDA), (MeEtCp)Nb(=NnPr)(nPentyl2~EDA), (MeEtCp)Nb(=NnPr)(tAm2-EDA), (MePrCp)Nb(=NnPr)(EDA), (MePrCp)Nb(=NnPr)(Me2-EDA), (MePrCp)Nb(=NnPr)(Et2- EDA), (MePrCp)Nb(=NnPr)(nPr2-EDA), (MePrCp)Nb(=NnPr)(iPr2-EDA), (MePrCp)Nb(=NnPr)(nBu2-EDA), (MePrCp)Nb(=NnPr)(tBu2”EDA), (MePrCp)Nb(=NnPr)(nPentyl2-EDA), (MePrCp)Nb(=NnPr)(tAm2-EDA), (Penta- MeCp)Nb(=NnPr)(EDA), (Penta-MeCp)Nb(=NnPr)(Me2-EDA), (Penta-
MeCp)Nb(=NnPr)(Et2-EDA), (Penta-MeCp)Nb(=NnPr)(nPr2-EDA), (Penta- MeCp)Nb(=NnPr)(iPr2-EDA), (Penta-MeCp)Nb(=NnPr)(nBu2-EDA), (Penta- MeCp)Nb(=NnPr)(tBu2-EDA), (Penta-MeCp)Nb(=NnPr)(nPentyl2-EDA), or (Penta- MeCp)Nb(=NnPr)(tAm2-EDA).
« the Group V (five)-containing film being an Nb2O5 film or an NbN film;
• the substrate being a Si wafer;
« the substrate being a crystalline silicon layer;
« the substrate being a powder substrate;
« the vapor deposition process being an ALD process or a CVD process;
« the vapor deposition process being a PEALD process or a spatial ALD process; and
« a deposition temperature ranging from approximately 50°C and approximately 600°C. [0012] Also disclosed is a Group V (five)-containing film forming composition for a vapor deposition process comprising a precursor having the formula:
wherein M is Group V (five) element, vanadium (V), niobium (Nb), or tantalum (Ta);
R1 to R8 each is H, a C1-C6 alkyl group, a fluoro group, an alkylsilyl group, a germyl group, an alkylamide or an aikylsilylamide; m = 1 to 5, n = 1 to 5. The disclosed methods may include one or more of the following aspects:
« R1 to R8 each being independently H, Me, Et, nPr, IPr, tBu, sBu, IBu, nBu, tAmyl, SiMe3, SiMe2H, or SiH2Me;
« the precursor being Niobium tButyl Imido Cyclopentadienyl tAmyl-Diazadienyl, CpNb(=NtBu)(tAm2-DAD);
* the Group V (five)-containing film forming composition comprising between approximately 95% w/w and approximately 100.0% w/w of the precursor;
« the Group V (five)-containing film forming composition comprising between 99,0% w/w to 100.0% w/w of the precursor;
« the Group V (five)-containing film forming composition comprising between approximately 0.0% w/w and approximately 5.0% w/w impurities.
[0013] Also disclosed is a method of forming an Nb2O5 film or coating by an ALD process on a substrate in a reaction chamber, the method comprising the steps of: a) exposing the substrate to a vapor of Niobium tButyl Imido Cyclopentadienyl tAmyl-Diazadienyl (CpNb(=NtBu)(tAm2-DAD)); b) exposing the substrate to an oxidizer; and c) repeating the steps of a) and b) until a desired thickness of the Nb2O5 film is deposited on the substrate using the ALD process. The disclosed methods may include one
or more of the following aspects:
* further comprising the steps of introducing an inert gas to purge th reaction chamber following the steps a) and b), respectively, to separate each exposure;
® the substrate being a powder;
* the powder comprising one or more of NMC (Lithium Nickel Manganese Cobalt Oxide), LCO (Lithium Cobalt Oxide), LFP (Lithium Iron Phosphate), and other battery cathode materials.
Notation and Nomenclature
[0014] The following detailed description and claims utilize a number of abbreviations, symbols, and terms, which are generally well known in the art.
[0015] As used herein, the indefinite article “a” or “an” means one or more.
[0016] As used herein, “about” or “around” or “approximately” in the text or in a claim means ±10% of the value stated.
[0017] As used herein, “room temperature” in the text or in a claim means from approximately 20°C to approximately 30°C.
[0018] The term “ambient temperature” refers to an environment temperature approximately 20°C to approximately 30°C.
[0019] The term “substrate” refers to a material or materials on which a process Is conducted. The substrate may refer to a wafer having a material or materials on which a process is conducted. The substrates may be any suitable wafer used in semiconductor, photovoltaic, flat panel, or LCD-TFT device manufacturing. The substrate may also have one or more layers of differing materials already deposited upon it from a previous manufacturing step. For example, the wafers may include silicon layers (e.g., crystalline, amorphous, porous, etc.), silicon containing layers (e.g., SiO2, SiN, SiON, SiCOH, etc.), metal containing layers (e.g., copper, cobalt, ruthenium, tungsten, platinum, palladium, nickel, ruthenium, gold, etc.) or combinations thereof. Furthermore, the substrate may be planar or patterned. The substrate may be an organic patterned photoresist film. The substrate may include layers of oxides which are used as dielectric materials in MEMS, 3D NAND, MIM, DRAM, or FeRam device applications (for example, ZrO2 based materials, HfO2 based materials, TIO2 based materials, AI2O3 based materials, rare earth oxide based materials, ternary oxide based materials, etc.) or nitride-based films (for example, TaN, TiN, NbN) that are used as electrodes. One of ordinary skill in the art will recognize that the terms “film” or “layer” used herein refer to a thickness of some material laid on or spread over a surface and that the
surface may be a trench or a line. Throughout the specification and claims, the wafer and any associated layers thereon are referred to as substrates.
[0020] The term “wafer" or “patterned wafer” refers to a wafer having a stack of films on a substrate and at least the top-most film having topographic features that have been created in steps prior to the deposition of the Group V (five)-containing film.
[0021] The term “aspect ratio” refers to a ratio of the height of a trench (or aperture) to the width of the trench (or the diameter of the aperture).
[0022] The term “high aspect ratio” refers to an aspect ratio larger than approximately 2:1 , preferably an aspect ratio ranging from approximately 2:1 to approximately 200:1.
[0023] Note that herein, the terms “film” and “layer” may be used interchangeably. It is understood that a film may correspond to, or related to a layer, and that the layer may refer to the film. Furthermore, one of ordinary skill in the art will recognize that the terms “film” or “layer used herein refer to a thickness of some material laid on or spread over a surface and that the surface may range from as large as the entire wafer to as small as a trench or a line. [0024] Note that herein, the terms “aperture”, “via”, “hole” and “trench” may be used interchangeably to refer to an opening formed in a semiconductor structure.
[0025] As used herein, the abbreviation "NAND" refers to a "Negative AND" or "Not AND" (electronic logic gate); the abbreviation "2D" refers to 2 dimensional gate structures on a planar substrate; the abbreviation "3D" refers to 3 dimensional or vertical gate structures, wherein the gate structures are stacked In the vertical direction.
[0026] Note that herein, the terms “deposition temperature” and “substrate temperature” may be used interchangeably. It is understood that a substrate temperature may correspond to, or be related to a deposition temperature, and that the deposition temperature may refer to the substrate temperature.
[0027] The term “film-forming composition” refers to a composition used for deposition of a film. The film-forming composition may include, but Is not limited to, a precursor, a solvent and/or a carrier gas. Furthermore, the film-forming composition may include, but is not limited to, a precursor, optionally a solvent, optionally a carrier gas, and optionally one or more co- reactant(s). Herein, the precursor may be supplied either in a neat form or in a blend with a suitable solvent. The precursor may be present in varying concentrations in the solvent. Alternatively, the precursor may be vaporized by passing a carrier gas into a container that contains the precursor or by bubbling the carrier gas into the precursor. The carrier gas and precursor are then introduced into a reactor as a vapor. The co-reactant may be an oxidizer, a reducing agent, a dilute gas, an additive, an inhibitor, an additional or a secondary precursor, etc., for assisting in formation of the film. Here an inert gas selected from N2, He,
Ar, Kr, Xe may be used as the carrier gas and/or the dilute gas.
[0028] Note that herein, the terms “precursor” and “deposition compound” and “deposition gas” may be used interchangeably when the precursor is in a gaseous state at room temperature and ambient pressure, it is understood that a precursor may correspond to, or be related to a deposition compound or deposition gas, and that the deposition compound or deposition gas may refer to the precursor.
[0029] The standard abbreviations of the elements from the periodic table of elements are used herein. It should be understood that elements may be referred to by these abbreviation (e.g., Si refers to silicon, N refers to nitrogen, O refers to oxygen, C refers to carbon, H refers to hydrogen, F refers to fluorine, etc.).
[0030] The unique CAS registry numbers (/.e., “CAS”) assigned by the Chemical Abstract Service are provided to identify the specific molecules disclosed.
[0031] As used herein, the term “hydrocarbon” refers to a saturated or unsaturated function group containing exclusively carbon and hydrogen atoms. As used herein, the term “alkyl group” refers to saturated functional groups containing exclusively carbon and hydrogen atoms. An alkyl group is one type of hydrocarbon. Further, the term “alkyl group” refers to linear, branched, or cyclic alkyl groups. Examples of linear alkyl groups include without limitation, methyl groups, ethyl groups, propyl groups, butyl groups, etc. Examples of branched alkyls groups include without limitation, t-butyl. Examples of cyclic alkyl groups include without limitation, cyclopropyl groups, cyclopentyl groups, cyclohexyl groups, etc. [0032] As used herein, the term “alkyl group” refers to saturated functional groups containing exclusively carbon and hydrogen atoms. Further, the term “alkyl group” refers to linear, branched, or cyclic alkyl groups. Examples of linear alkyl groups include without limitation, methyl groups, ethyl groups, propyl groups, butyl groups, etc. Examples of branched alkyls groups include without limitation, t-butyl. Examples of cyclic alkyl groups include without limitation, cyclopropyl groups, cyclopentyl groups, cyclohexyl groups, etc. [0033] As used herein, the abbreviation “Me” refers to a methyl group; the abbreviation “Et” refers to an ethyl group; the abbreviation “Pr” refers to a propyl group; the abbreviation “nPr” refers to a “normal” or linear propyl group; the abbreviation “IPr” refers to an isopropyl group; the abbreviation “Bu” refers to a butyl group; the abbreviation “nBu” refers to a “normal” or linear butyl group; the abbreviation “tBu” refers to a tert-butyl group, also known as 1 ,1- dimethylethyl; the abbreviation “sBu” refers to a sec-butyl group, also known as 1- methylpropyl; the abbreviation “IBu” refers to an iso-butyl group, also known as 2- methylpropyl; the abbreviation “amyl” refers to an amyl or pentyl group; the abbreviation “tAmyl” refers to a tert-amyl group, also known as 1 ,1 -dimethylpropyl.
[0034] Ptease note that the metal-containing (V, Nb and Ta) films or layers deposited, such as niobium oxide or niobium nitride, may be listed throughout the specification and claims without reference to their proper stoichiometry (e.g., NbO = Nb2O5). These layers may also contain Hydrogen, typically from 0 atomic % to 15 atomic %. However, since not routinely measured, any film compositions given ignore their H content, unless explicitly stated otherwise. Furthermore, the concentration of hydrogen may be further tuned by performing post deposition annealing to obtained desired thin film properties.
[0035] Ranges may be expressed herein as from about one particular value, and/or to about another particular value. When such a range is expressed, it is to be understood that another embodiment is from the one particular value and/or to the other particular value, along with all combinations within said range. Any and all ranges recited herein are inclusive of their endpoints (i.e. , x~1 to 4 or x ranges from 1 to 4 includes x=1 , x=4, and x=any number in between), irrespective of whether the term “inclusively” is used.
[0036] As used herein, the formula, (R3R4R5R6R7Cp)Nb(= NR1)(R22-DAD), is represented by the following structure:
wherein DAD = Diazadiene; R1 = tBu or nPr ; R2 = Me, Et, nPr, IPr, nBu, tBu, nPentyl ortAm: R3, R4, R5, R6 and R7 each is Independently H, Me, Et, nPr, iPr, nBu, tBu or sBu.
[0037] As used herein, the formula, (R3R4R5R6R7Cp)Nb(=NR1)(R2 2-EDA), is represented by the following structure:
wherein EDA is Ethylenediamine; R1 is tBu or nPr ; R2 is Me, Et, nPr, iPr, nBu, tBu, nPentyl or tAm; R3, R4, R5, R6 and R7 each is Independently H, Me, Et, nPr, IPr, nBu, tBu or sBu.
[0038] Reference herein to “one embodiment” or “an embodiment” means that a particular feature, structure, or characteristic described in connection with the embodiment
may be included in at least one embodiment of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments necessarily mutually exclusive of other embodiments. The same applies to the term “implementation.”
[0039] As used herein, the term “independently” when used in the context of describing R groups should be understood to denote that the subject R group is not only independently selected relative to other R groups bearing the same or different subscripts or superscripts, but is also independently selected relative to any additional species of that same R group. For example in the formula MR1, (NR2R3)(4-x:), where x is 2 or 3, the two or three R1 groups may, but need not be identical to each other or to R2 or to R3. Further, it should be understood that unless specifically stated otherwise, values of R groups are independent of each other when used in different formulas.
[0040] As used in this application, the word “exemplary” is used herein to mean serving as an example, instance, or illustration. Any aspect or design described herein as “exemplary” is not necessarily to be construed as preferred or advantageous over other aspects or designs. Rather, use of the word exemplary is intended to present concepts in a concrete fashion.
[0041] Additionally, the term "or” is intended to mean an inclusive “or” rather than an exclusive “or”. That is, unless specified otherwise, or clear from context, “X employs A or B” is intended to mean any of the natural inclusive permutations. That is, if X employs A; X employs B; or X employs both A and B, then “X employs A or B” is satisfied under any of the foregoing instances. In addition, the articles “a” and “an” as used in this application and the appended claims should generally be construed to mean “one or more” unless specified otherwise or clear from context to be directed to a singular form.
[0042] "Comprising" in a claim is an open transitional term which means the subsequently identified claim elements are a nonexclusive listing (i.e., anything else may be additionally included and remain within the scope of “comprising”). “Comprising” is defined herein as necessarily encompassing the more limited transitional terms "consisting essentially of" and “consisting of; “comprising” may therefore be replaced by "consisting essentially of or “consisting of” and remain within the expressly defined scope of “comprising”.
[0043] “Providing” in a claim is defined to mean furnishing, supplying, making available, or preparing something. The step may be performed by any actors in the absence of express language in the claim to the contrary.
Brief Description of the Drawings
[0044] Other aspects, features, and advantages of the present invention will become more fully apparent from the following detailed description, the appended claims, and the accompanying drawings in which like reference numerals identify similar or identical elements.
FIG. 1 is a Thermo Gravimetric Analysis (TGA) graph demonstrating the percentage of weight with increasing temperature of Niobium tButyl imido cyclopentadienyl tAmyl- diazadienyl, CpNb(=NtBu)(tAm2-DAD);
FIG. 2 is a Differential scanning calorimetry (DSC) of CpNb(=NtBu)(tAm2"DAD);
FIG. 3 is ALD window of CpNb(=NtBu)(tAm2-DAD);
FIG. 4a is a full image of step coverage of patterned wafer of Nb2O5 film at 325°C by SEM;
FIG. 4b is a top image of FIG. 4a;
FIG. 4c is a bottom image of FIG. 4a; and
FIG. 5 is a XPS depth profile plot of Nb2O5 film at 325°C.
Description of Preferred Embodiments
[0045] Disclosed are Group V (five) (V, Nb, Ta) metal containing films forming compositions, methods of synthesizing the same, and methods of forming Group V metal containing films on one or more substrates via ALD (atomic layer deposition processes) using the Group V metal containing film forming compositions.
[0046] The disclosed Group V element-containing film forming compositions comprise Group V element-containing precursors having the formula:
wherein M is Group V (five) element, vanadium (V), niobium (Nb), or tantalum (Ta); R1 to R8 each is H, a C1-C5 alkyl group, a fluoro group, an alkylsilyl group, a germyl group, an alkylamide or an alkylsilylamide; m = 1 to 5, n ~ 1 to 5. As illustrated in the above formula, the nitrogen atoms and a cyclopentadienyl ring may be bonded to the center Group V atom M, resulting in a tetracoordinate M(V) center. The resulting geometry may be pseudo tetrahedral.
[0047] The disclosed Group V element-containing precursors offer high thermal stability by chelating effect of bidentate ligand which has linkage between two amines, when compared to NbCp(=NtBu)(NMe2)2 that has no bidentate ligand.
[0048] Exemplary Group V element-containing precursors from formula (I) include: (R3~ 7Cp)Nb(=NR1)(R2 2-DAD),
wherein DAD = Diazadiene; R1 = tBu or nPr ; R2 = Me, Et, nPr, iPr, nBu, tBu, nPentyl or tAm; R3, R4, R5, R6 and R7 each is independently H, Me, Et, nPr, iPr, nBu, tBu or sBu. Here R3’7 represents R3R4R5R5R7. More specifically, (R3-7Cp)Nb(=NR1 )(R2 2-DAD) includes (Cp)Nb(=NtBu)(Me2-DAD), (Cp)Nb(=NtBu)(Et2-DAD), (Cp)Nb(=NtBu)(nPr2-DAD), (Cp)Nb(=NtBu)(iPr2-DAD), (Cp)Nb(~NtBu)(nBu2-DAD), (Cp)Nb(=NtBu)(tBu2-DAD), (Cp)Nb(=NtBu)(nPentyl2-DAD), (Cp)Nb(=NtBu)(tAm2-DAD), (MeCp)Nb(=NtBu)(Me2-DAD), (MeCp)Nb(=NtBu)(Et2-DAD), (MeCp)Nb(=NtBu)(nPr2-DAD), (MeCp)Nb(=NtBu)(iPr2-DAD), (MeCp)Nb(=NtBu)(nBu2-DAD), (MeCp)Nb(=NtBu)(tBu2-DAD), (MeCp)Nb(=NtBu)(nPentyl2-
DAD), (EtCp)Nb(~NtBu)(nPr2~DAD), (EtCp)Nb(=NtBu)(iPr2-DAD), (EtCp)Nb(=NtBu)(nBu2-
DAD), (EtCp)Nb(=NtBu)(tBu2-DAD), (EtCp)Nb(=NtBu)(nPentyi2-DAD),
(EtCp)Nb(=NtBu)(tAm2-DAD)i (nPrCp)Nb(=NtBu)(Me2-DAD), (nPrCp)Nb(=NtBu)(Et2-DAD)i
(nPrCp)Nb(=NtBu)(nPr2-DAD), (nPrCp)Nb(=NtBu)(iPr2-DAD), (nPrCp)Nb(=NtBu)(nBu2-
DAD), (nPrCp)Nb(=NtBu)(tBu2-DAD), (nPrCp)Nb(=NtBu)(nPentyl2-DAD),
(nPrCp)Nb(=NtBu)(tAm2-DAD), (iPrCp)Nb(=NtBu)(Me2-DAD), (iPrCp)Nb(=NtBu)(Et2-DAD),
(iPrCp)Nb(=NtBu)(nPr2-DAD), (iPrCp)Nb(=NtBu)(iPr2-DAD), (iPrCp)Nb(=NtBu)(nBu2-DAD),
(iPrCp)Nb(=NtBu)(tBu2-DAD), (iPrCp)Nb(=NtBu)(nPentyl2-DAD), (iPrCp)Nb(=NtBu)(tAm2-
DAD), (nBuCp)Nb(=NtBu)(Me2-DAD), (nBuCp)Nb(=NtBu)(Et2-DAD),
(nBuCp)Nb(=NtBu)(nPr2-DAD), (nBuCp)Nb(=NtBu)(iPr2-DAD), (nBuCp)Nb(=NtBu)(nBu2-
DAD), (nBuCp)Nb(=NtBu)(tBu2-DAD), (nBuCp)Nb(=NtBu)(nPentyl2-DAD),
(nBuCp)Nb(=NtBu)(tAm2-DAD), (tBuCp)Nb(=NtBu)(Me2-DAD), (tBuCp)Nb(=NtBu)(Et2-
DAD), (tBuCp)Nb(=NtBu)(nPr2-DAD), (tBuCp)Nb(=NtBu)(iPr2-DAD),
(tBuCp)Nb(=NtBu)(nBu2-DAD), (tBuCp)Nb(=NtBu)(tBu2-DAD), (tBuCp)Nb(=NtBu)(nPentyl2-
DAD), (tBuCp)Nb(=NtBu)(tAm2-DAD), (sBuCp)Nb(~NtBu)(Me2-DAD),
(sBuCp)Nb(=NtBu)(Et2-DAD), (sBuCp)Nb(=NtBu)(nPr2-DAD), (sBuCp)Nb(=NtBu)(iPr2-
DAD), (sBuCp)Nb(=NtBu)(nBu2-DAD)! (sBuCp)Nb(=NtBu)(tBu2-DAD),
(sBuCp)Nb(=NtBu)(nPentyl2~DAD)! (sBuCp)Nb(=NtBu)(tAm2-DAD), (Di-
MeCp)Nb(=NtBu)(Me2-DAD), (Di-MeCp)Nb(=NtBu)(Et2-DAD), (Di-MeCp)Nb(=NtBu)(nPr2-
DAD), (Di-MeCp)Nb(=NtBu)(iPr2-DAD), (Di-MeCp)Nb(=NtBu)(nBu2-DAD), (Di-
MeCp)Nb(=NtBu)(tBu2~DAD)! (Di-MeCp)Nb(=NtBu)(nPentyi2-DAD), (Di-
MeCp)Nb(=NtBu)(tAm2-DAD), (MeEtCp)Nb(=NtBu)(Me2-DAD), (MeEtCp)Nb(=NtBu)(Et2-
DAD), (MeEtCp)Nb(=NtBu)(nPr2-DAD), (MeEtCp)Nb(=NtBu)(iPr2-DAD),
(MeEtCp)Nb(=NtBu)(nBu2-DAD), (MeEtCp)Nb(=NtBu)(tBu2”DAD),
(MeEtCp)Nb(=NtBu)(nPentyl2-DAD), (MeEtCp)Nb(=NtBu)(tAm2-DAD),
(MePrCp)Nb(=NtBu)(Me2-DAD), (MePrCp)Nb(=NtBu)(Et2-DAD), (MePrCp)Nb(=NtBu)(nPr2-
DAD), (MePrCp)Nb(=NtBu)(iPr2-DAD), (MePrCp)Nb(=NtBu)(nBu2-DAD),
(MePrCp)Nb(=NtBu)(tBu2-DAD), (MePrCp)Nb(=NtBu)(nPentyl2-DAD),
(MePrCp)Nb(=NtBu)(tAm2-DAD), (Penta-MeCp)Nb(=NtBu)(Me2-DAD), (Penta-
MeCp)Nb(=NtBu)(Et2-DAD), (Penta-MeCp)Nb(=NtBu)(nPr2-DAD), (Penta-
MeCp)Nb(=NtBu)(iPr2-DAD), (Penta-MeCp)Nb(=NtBu)(nBu2-DAD), (Penta-
MeCp)Nb(=NtBu)(tBu2-DAD), (Penta-MeCp)Nb(=NtBu)(nPentyi2-DAD), (Penta-
MeCp)Nb(=NtBu)(tAm2-DAD), (Cp)Nb(=NnPr)(Me2-DAD), (Cp)Nb(=NnPr)(Et2-DAD),
(Cp)Nb(=NnPr)(nPr2-DAD), (Cp)Nb(=NnPr)(iPr2-DAD), (Cp)Nb(=NnPr)(nBu2-DAD),
(Cp)Nb(=NnPr)(tBu2-DAD), (Cp)Nb(=NnPr)(nPentyi2-DAD), (Cp)Nb(=NnPr)(tAm2-DAD),
(MeCp)Nb(=NnPr)(Me2-DAD), (MeCp)Nb(=NnPr)(Et2-DAD), (MeCp)Nb(=NnPr)(nPr2-DAD), (MeCp)Nb(=NnPr)(iPr2-DAD)1 (MeCp)Nb(=NnPr)(nBu2-DAD), (MeCp)Nb(=NnPr)(tBu2- DAD), (MeCp)Nb(=NnPr)(nPentyl2-DAD), (MeCp)Nb(=NnPr)(tAm2-DAD), (EtCp)Nb(~NnPr)(Me2-DAD), (EtCp)Nb(=NnPr)(Et2-DAD), (EtCp)Nb(=NnPr)(nPr2-DAD), (EtCp)Nb(=NnPr)(iPr2-DAD), (EtCp)Nb(=NnPr)(nBu2-DAD), (EtCp)Nb(=NnPr)(tBu2-DAD)!
(EtCp)Nb(=NnPr)(nPentyi2-DAD), (EtCp)Nb(=NnPr)(tAm2-DAD), (nPrCp)Nb(=NnPr)(Me2- DAD), (nPrCp)Nb(=NnPr)(Et2-DAD), (nPrCp)Nb(=NnPr)(nPr2-DAD),
(nPrCp)Nb(=NnPr)(iPr2-DAD), (nPrCp)Nb(=NnPr)(nBu2-DAD), (nPrCp)Nb(=NnPr)(tBu2-
DAD), (nPrCp)Nb(=NnPr)(nPentyl2-DAD), (nPrCp)Nb(=:NnPr)(tAm2-DAD), (iPrCp)Nb(=NnPr)(Me2-DAD), (iPrCp)Nb(=NnPr)(Et2-DAD), (iPrCp)Nb(=NnPr)(nPr2-DAD), (iPrCp)Nb(=NnPr)(iPr2-DAD), (iPrCp)Nb(=NnPr)(nBu2-DAD), (iPrCp)Nb(=NnPr)(tBu2-DAD), (iPrCp)Nb(=NnPr)(nPentyl2-DAD), (iPrCp)Nb(=NnPr)(tAm2-DAD), (nBuCp)Nb(=NnPr)(Me2-
DAD), (nBuCp)Nb(=NnPr)(Et2-DAD), (nBuCp)Nb(=NnPr)(nPr2-DAD), (nBuCp)Nb(=NnPr)(iPr2-DAD), (nBuCp)Nb(=NnPr)(nBu2-DAD), (nBuCp)Nb(=NnPr)(tBu2-
DAD), (nBuCp)Nb(=NnPr)(nPentyi2-DAD), (nBuCp)Nb(=NnPr)(tAm2-DAD), (tBuCp)Nb(=NnPr)(Me2-DAD), (tBuCp)Nb(=NnPr)(Et2-DAD), (tBuCp)Nb(=NnPr)(nPr2-DAD), (tBuCp)Nb(=NnPr)(iPr2-DAD), (tBuCp)Nb(=NnPr)(nBu2-DAD): (tBuCp)Nb(=NnPr)(tBu2- DAD), (tBuCp)Nb(=NnPr)(nPentyl2~DAD), (tBuCp)Nb(=NnPr)(tAm2-DAD)!
(sBuCp)Nb(=NnPr)(Me2-DAD), (sBuCp)Nb(=NnPr)(Et2-DAD), (sBuCp)Nb(=NnPr)(nPr2-
DAD), (sBuCp)Nb(=NnPr)(iPr2-DAD), (sBuCp)Nb(=NnPr)(nBu2-DAD), (sBuCp)Nb(=NnPr)(tBu2-DAD), (sBuCp)Nb(=NnPr)(nPentyl2-DAD), (sBuCp)Nb(=NnPr)(tAm2-DAD), (Di-MeCp)Nb(=NnPr)(Me2-DAD), (Di-
MeCp)Nb(=NnPr)(Et2-DAD), (Di-MeCp)Nb(=NnPr)(nPr2-DAD), (Di-MeCp)Nb(=NnPr)(iPr2- DAD), (Di-MeCp)Nb(=NnPr)(nBu2-DAD)> (Di~MeCp)Nb(~NnPr)(tBu2~DAD), (Di-
MeCp)Nb(=NnPr)(nPentyl2-DAD), (Di-MeCp)Nb(=NnPr)(tAm2-DAD), (MeEtCp)Nb(=NnPr)(Me2-DAD), (MeEtCp)Nb(=NnPr)(Et2-DAD)i (MeEtCp)Nb(=NnPr)(nPr2-
DAD), (MeEtCp)Nb(=NnPr)(iPr2-DAD), (MeEtCp)Nb(=NnPr)(nBu2~DAD), (MeEtCp)Nb(=NnPr)(tBu2-DAD), (MeEtCp)Nb(=NnPr)(nPentyl2-DAD), (MeEtCp)Nb(=NnPr)(tAm2-DAD), (MePrCp)Nb(=NnPr)(Me2-DAD), (MePrCp)Nb(=NnPr)(Et2-DAD), (MePrCp)Nb(=NnPr)(nPr2-DAD): (MePrCp)Nb(=NnPr)(iPr2-
DAD), (MePrCp)Nb(=NnPr)(nBu2-DAD), (MePrCp)Nb(=NnPr)(tBu2-DAD), (MePrCp)Nb(=NnPr)(nPentyl2-DAD), (MePrCp)Nb(=NnPr)(tAm2-DAD), (Penta- MeCp)Nb(=NnPr)(Me2-DAD), (Penta-MeCp)Nb(=NnPr)(Et2-DAD), (Penta- MeCp)Nb(=NnPr)(nPr2-DAD), (Penta-MeCp)Nb(=NnPr)(iPr2-DAD), (Penta-
MeCp)Nb(=NnPr)(nBu2-DAD), (Penta-MeCp)Nb(~NnPr)(tBu2-DAD), (Penta- MeCp)Nb(=NnPr)(nPentyl2-DAD), or (Penta-MeCp)Nb(=NnPr)(tAm2-DAD).
[0049] Exemplary Group V (five) element-containing precursors from formula (II) include: (R3-7Cp)Nb(=NR1)(R2 2-EDA),
wherein EDA is Ethylenediamine; R1 = tBu or nPr ; R2 = Me, Et, nPr, iPr, nBu, tBu, nPentyl or tAm; R3, R4, R5, R6 and R7 each is Independently H, Me, Et, nPr, iPr, nBu, tBu or sBu. Here R3'7 represents R3R4R5R6R7. More specifically, (R3’7Cp)Nb(=NR1)(R22“EDA) includes (Cp)Nb(=NtBu)(EDA), (Cp)Nb(=NtBu)(Me2-EDA), (Cp)Nb(=NtBu)(Et2-EDA), (Cp)Nb(=NtBu)(nPr2-EDA), (Cp)Nb(=NtBu)(iPr2-EDA), (Cp)Nb(=NtBu)(nBu2-EDA), (Cp)Nb(=NtBu)(tBu2-EDA), (Cp)Nb(=NtBu)(nPentyl2-EDA), (Cp)Nb(=NtBu)(tAm2-EDA), (MeCp)Nb(=NtBu)(EDA), (MeCp)Nb(=NtBu)(Me2-EDA), (MeCp)Nb(=NtBu)(Et2-EDA), (MeCp)Nb(=NtBu)(nPr2-EDA), (MeCp)Nb(=NtBu)(iPr2-EDA), (MeCp)Nb(=NtBu)(nBu2-EDA), (MeCp)Nb(=NtBu)(tBu2-EDA), (MeCp)Nb(=NtBu)(nPentyl2-EDA), (MeCp)Nb(=NtBu)(tAm2- EDA), (EtCp)Nb(=NtBu)(EDA), (EtCp)Nb(=NtBu)(Me2-EDA), (EtCp)Nb(=NtBu)(Et2-EDA), (EtCp)Nb(=NtBu)(nPr2-EDA), (EtCp)Nb(=NtBu)(iPr2-EDA), (EtCp)Nb(=NtBu)(nBu2-EDA), (EtCp)Nb(==NtBu)(tBu2-EDA), (EtCp)Nb(=:NtBu)(nPentyl2-EDA), (EtCp)Nb(=NtBu)(tAm2- EDA), (nPrCp)Nb(=NtBu)(EDA), (nPrCp)Nb(=NtBu)(Me2-EDA), (nPrCp)Nb(=NtBu)(Et2- EDA), (nPrCp)Nb(=NtBu)(nPr2-EDA), (nPrCp)Nb(=NtBu)(iPr2-EDA), (nPrCp)Nb(=NtBu)(nBu2-EDA), (nPrCp)Nb(=NtBu)(tBu2-EDA), (nPrCp)Nb(=NtBu)(nPentyl2- EDA), (nPrCp)Nb(=NtBu)(tAm2-EDA), (iPrCp)Nb(=NtBu)(EDA), (iPrCp)Nb(=NtBu)(Me2- EDA), (iPrCp)Nb(=NtBu)(Et2-EDA), (iPrCp)Nb(=NtBu)(nPr2-EDA), (iPrCp)Nb(=NtBu)(iPr2- EDA), (iPrCp)Nb(=NtBu)(nBu2-EDA), (iPrCp)Nb(=NtBu)(tBu2-EDA), (iPrCp)Nb(=NtBu)(nPentyl2-EDA), (iPrCp)Nb(=NtBu)(tAm2-EDA), (nBuCp)Nb(=NtBu)(EDA), (nBuCp)Nb(=NtBu)(Me2-EDA), (nBuCp)Nb(=NtBu)(Et2-EDA), (nBuCp)Nb(=NtBu)(nPr2- EDA), (nBuCp)Nb(=NtBu)(iPr2-EDA), (nBuCp)Nb(=NtBu)(nBu2-EDA), (nBuCp)Nb(=NtBu)(tBu2-EDA), (nBuCp)Nb(=NtBu)(nPentyl2-EDA), (nBuCp)Nb(=NtBu)(tAm2-EDA), (tBuCp)Nb(=NtBu)(EDA), (tBuCp)Nb(=NtBu)(Me2-EDA), (tBuCp)Nb(=NtBu)(Et2-EDA), (tBuCp)Nb(=NtBu)(nPr2-EDA), (tBuCp)Nb(=NtBu)(iPr2-EDA), (tBuCp)Nb(=NtBu)(nBu2-EDA), (tBuCp)Nb(=NtBu)(tBu2-EDA), (tBuCp)Nb(=NtBu)(nPentyl2-
EDA), (tBuCp)Nb(=NtBu)(tAm2”EDA)! (sBuCp)Nb(=NtBu)(EDA), (sBuCp)Nb(~NtBu)(Me2~ EDA), (sBuCp)Nb(=NtBu)(Et2-EDA), (sBuCp)Nb(=NtBu)(nPr2-EDA), (sBuCp)Nb(=NtBu)(iPr2-EDA), (sBuCp)Nb(=NtBu)(nBu2-EDA), (sBuCp)Nb(=NtBu)(tBu2- EDA), (sBuCp)Nb(=NtBu)(nPentyi2~EDA), (sBuCp)Nb(=NtBu)(tAm2-EDA), (Di- MeCp)Nb(=NtBu)(EDA), (Di-MeCp)Nb(=NtBu)(Me2-EDA), (Di-MeCp)Nb(=NtBu)(Et2-EDA), (Di-MeCp)Nb(=NtBu)(nPr2-EDA), (Di-MeCp)Nb(=NtBu)(iPr2-EDA), (Di- MeCp)Nb(=NtBu)(nBu2-EDA), (Di-MeCp)Nb(=NtBu)(tBu2-EDA), (Di- MeCp)Nb(=NtBu)(nPentyl2-EDA), (Di-MeCp)Nb(=NtBu)(tAm2-EDA), (MeEtCp)Nb(=NtBu)(EDA), (MeEtCp)Nb(=NtBu)(Me2-EDA), (MeEtCp)Nb(=NtBu)(Et2-EDA), (MeEtCp)Nb(=NtBu)(nPr2-EDA), (MeEtCp)Nb(=NtBu)(iPr2-EDA), (MeEtCp)Nb(=NtBu)(nBu2-EDA), (MeEtCp)Nb(=NtBu)(tBu2-EDA), (MeEtCp)Nb(=NtBu)(nPentyl2-EDA), (MeEtCp)Nb(=NtBu)(tAm2-EDA), (MePrCp)Nb(=NtBu)(EDA), (MePrCp)Nb(=NtBu)(Me2-EDA), (MePrCp)Nb(=NtBu)(Et2- EDA), (MePrCp)Nb(=NtBu)(nPr2-EDA), (MePrCp)Nb(=NtBu)(iPr2-EDA), (MePrCp)Nb(=NtBu)(nBu2-EDA), (MePrCp)Nb(=NtBu)(tBu2-EDA), (MePrCp)Nb(=NtBu)(nPenty!2-EDA), (MePrCp)Nb(=NtBu)(tAm2-EDA), (Penta- MeCp)Nb(=NtBu)(EDA), (Penta-MeCp)Nb(=NtBu)(Me2-EDA), (Penta-MeCp)Nb(=NtBu)(Et2- EDA), (Penta-MeCp)Nb(=NtBu)(nPr2-EDA), (Penta-MeCp)Nb(=NtBu)(iPr2-EDA), (Penta- MeCp)Nb(=NtBu)(nBu2-EDA), (Penta-MeCp)Nb(=NtBu)(tBu2-EDA), (Penta- MeCp)Nb(=NtBu)(nPentyl2"EDA), (Penta-MeCp)Nb(=NtBu)(tAm2-EDA), (Cp)Nb(=NnPr)(EDA), (Cp)Nb(=NnPr)(Me2-EDA), (Cp)Nb(=NnPr)(Et2-EDA), (Cp)Nb(=NnPr)(nPr2-EDA), (Cp)Nb(=NnPr)(iPr2-EDA), (Cp)Nb(=NnPr)(nBu2-EDA), (Cp)Nb(=NnPr)(tBu2-EDA), (Cp)Nb(=NnPr)(nPentyi2-EDA), (Cp)Nb(=NnPr)(tAm2-EDA), (MeCp)Nb(=NnPr)(EDA), (MeCp)Nb(=NnPr)(Me2-EDA), (MeCp)Nb(=NnPr)(Et2~EDA), (MeCp)Nb(=NnPr)(nPr2-EDA), (MeCp)Nb(=NnPr)(iPr2-EDA), (MeCp)Nb(=NnPr)(nBu2- EDA), (MeCp)Nb(=NnPr)(tBu2-EDA), (MeCp)Nb(=NnPr)(nPentyl2-EDA), (MeCp)Nb(=NnPr)(tAm2-EDA), (EtCp)Nb(=NnPr)(EDA), (EtCp)Nb(=NnPr)(Me2-EDA), (EtCp)Nb(=NnPr)(Et2-EDA), (EtCp)Nb(=NnPr)(nPr2-EDA), (EtCp)Nb(=NnPr)(iPr2-EDA), (EtCp)Nb(=NnPr)(nBu2-EDA), (EtCp)Nb(=NnPr)(tBu2-EDA), (EtCp)Nb(=NnPr)(nPenty!2- EDA), (EtCp)Nb(=NnPr)(tAm2-EDA), (nPrCp)Nb(=NnPr)(EDA), (nPrCp)Nb(=NnPr)(Me2~ EDA), (nPrCp)Nb(=NnPr)(Et2-EDA), (nPrCp)Nb(=NnPr)(nPr2-EDA),
(nPrCp)Nb(=NnPr)(iPr2-EDA), (nPrCp)Nb(=NnRr)(nBu2-EDA): (nPrCp)Nb(=NnPr)(tBu2- EDA), (nPrCp)Nb(=NnPr)(nPentyl2-EDA), (nPrCp)Nb(=NnPr)(tAm2-EDA), (iPrCp)Nb(=NnPr)(EDA), (iPrCp)Nb(=NnPr)(Me2-EDA), (iPrCp)Nb(=NnPr)(Et2-EDA), (jPrCp)Nb(=NnPr)(nPr2-EDA), (iPrCp)Nb(=NnPr)(iPr2-EDA), (iPrCp)Nb(=NnPr)(nBu2-EDA),
(jPrCp)Nb(=NnPr)(tBu2-EDA), (IPrCp)Nb(=NnPr)(nPentyl2-EDA)! (iPrCp)Nb(=NnPr)(tAm2- EDA), (nBuCp)Nb(=NnPr)(EDA), (nBuCp)Nb(=NnPr)(Me2-EDA), (nBuCp)Nb(=NnPr)(Et2- EDA), (nBuCp)Nb(=NnPr)(nPr2-EDA), (nBuCp)Nb(=NnPr)(iPr2-EDA), (nBuCp)Nb(=NnPr)(nBu2-EDA), (nBuCp)Nb(=NnPr)(tBu2-EDA), (nBuCp)Nb(=NnPr)(nPentyl2-EDA), (nBuCp)Nb(=NnPr)(tAm2-EDA), (tBuCp)Nb(=NnPr)(EDA), (tBuCp)Nb(=NnPr)(Me2-EDA)! (tBuCp)Nb(=NnPr)(Et2-EDA), (tBuCp)Nb(=NnPr)(nPr2-EDA), (tBuCp)Nb(=NnPr)(iPr2-EDA), (tBuCp)Nb(=NnPr)(nBu2- EDA), (tBuCp)Nb(=NnPr)(tBu2-EDA), (tBuCp)Nb(=NnPr)(nPentyl2-EDA), (tBuCp)Nb(=NnPr)(tAm2-EDA), (sBuCp)Nb(=NnPr)(EDA), (sBuCp)Nb(=NnPr)(Me2-EDA), (sBuCp)Nb(=NnPr)(Et2-EDA), (sBuCp)Nb(=NnPr)(nPr2-EDA), (sBuCp)Nb(=NnPr)(iPr2- EDA), (sBuCp)Nb(=NnPr)(nBu2-EDA), (sBuCp)Nb(=NnPr)(tBu2-EDA), (sBuCp)Nb(=NnPr)(nPentyl2-EDA), (sBuCp)Nb(=NnPr)(tAm2-EDA), (Di-
MeCp)Nb(=NnPr)(EDA), (Di-MeCp)Nb(=NnPr)(Me2-EDA), (Di-MeCp)Nb(=NnPr)(Et2-EDA), (Di-MeCp)Nb(=NnPr)(nPr2-EDA), (Di-MeCp)Nb(=NnPr)(iPr2-EDA), (Di- MeCp)Nb(=NnPr)(nBu2-EDA), (Di-MeCp)Nb(=NnPr)(tBu2-EDA), (Di~ MeCp)Nb(=NnPr)(nPentyl2-EDA), (Di-MeCp)Nb(=NnPr)(tAm2-EDA), (MeEtCp)Nb(=NnPr)(EDA), (MeEtCp)Nb(=NnPr)(Me2-EDA), (MeEtCp)Nb(=NnPr)(Et2- EDA), (MeEtCp)Nb(=NnPr)(nPr2-EDA)> (MeEtCp)Nb(=NnPr)(iPr2-EDA), (MeEtCp)Nb(=NnPr)(nBu2-EDA), (MeEtCp)Nb(=NnPr)(tBu2-EDA), (MeEtCp)Nb(=:NnPr)(nPentyh-EDA)i (MeEtCp)Nb(=:NnPr)(tAm2-EDA), (MePrCp)Nb(=NnPr)(EDA), (MePrCp)Nb(=NnPr)(Me2-EDA), (MePrCp)Nb(=NnPr)(Et2" EDA), (MePrCp)Nb(=NnPr)(nPr2-EDA), (MePrCp)Nb(=NnPr)(iPr2-EDA), (MePrCp)Nb(=NnPr)(nBu2~EDA), (MePrCp)Nb(=NnPr)(tBu2-EDA), (MePrCp)Nb(=NnPr)(nPentyl2-EDA), (MePrCp)Nb(=NnPr)(tAm2~EDA), (Penta- MeCp)Nb(=NnPr)(EDA), (Penta-MeCp)Nb(=NnPr)(Me2-EDA), (Penta- MeCp)Nb(=NnPr)(Et2-EDA), (Penta-MeCp)Nb(=NnPr)(nPr2-EDA), (Penta- MeCp)Nb(=NnPr)(iPr2-EDA), (Penta-MeCp)Nb(=NnPr)(nBu2-EDA), (Penta-
MeCp)Nb(=NnPr)(tBu2-EDA)s (Penta-MeCp)Nb(=NnPr)(nPentyl2-EDA)! or (Penta- MeCp)Nb(=NnPr)(tAm2-EDA).
[0050] More preferably, the disclosed precursor is Niobium tButyl Imido Cyclopentadienyl tAmyl-Diazadienyl, CpNb(=NtBu)(tAm2-DAD). This precursor may be synthesized by reacting lithium tAmyl-Diazadienyl with Nb(=NtBu)Cl3(py)2 and Sodium Cyclopentadienyl in THF.
[0051] The disclosed precursors have the flowing advantages. The disclosed precursors have high thermal stability, so that a high deposition temperature and a broad ALD window
are expected, in addition, the disclosed precursors are liquid precursors and therefore easier for vaporization and vapor delivery.
[0052] Purity of the disclosed Group V-containing film forming composition is greater than 95% w/w (i.e. , 95.0% w/w to 100.0% w/w), preferably greater than 98% w/w (i.e. , 98.0% w/w to 100.0% w/w), and more preferably greater than 99% w/w (i.e., 99.0% w/w to 100.0% w/w). One of ordinary skill in the art will recognize that the purity may be determined by H NMR and gas liquid chromatography with mass spectrometry. The disclosed Group V-containing film forming compositions may contain any of the following impurities: pyrazoles; pyridines; alkylamines; alkylimines; THF; ether; pentane; cyclohexane; heptanes; benzene; toluene: chlorinated metal compounds; lithium, sodium, potassium pyrazolyl. The total quantity of these impurities is preferably below 5% w/w (i.e., 0.0% w/w to 5.0% w/w), preferably below 2% w/w (i.e., 0.0% w/w to 2.0% w/w), and more preferably below 1 % w/w (i.e., 0.0% w/w to 1.0% w/w). The composition may be purified by recrystallisation, sublimation, distillation, and/or passing the gas liquid through a suitable adsorbent, such as a 4A molecular sieve.
[0053] Purification of the disclosed Group V-containing film forming composition may also result in metal impurities at the 0 ppbw to 1 ppmw, preferably 0-500 ppbw (part per billion weight) level. These metal impurities may include, but are not limited to, Aluminum (Al), Arsenic (As), Barium (Ba), Beryllium (Be), Bismuth (Bi), Cadmium (Cd), Calcium (Ca), Chromium (Cr), Cobalt (Co), Copper (Cu), Gallium (Ga), Germanium (Ge), Hafnium (Hf), Zirconium (Zr), Indium (In), Iron (Fe), Lead (Pb), Lithium (Li), Magnesium (Mg), Manganese (Mn), Tungsten (W), Nickel (Ni), Potassium (K), Sodium (Na), Strontium (Sr), Thorium (Th), Tin (Sn), Titanium (Ti), Uranium (U), and Zinc (Zn).
[0054] Also disclosed are methods for forming Group V-containing layers on a substrate using a vapor deposition process. Applicants believe, and demonstrate in the Deposition Example that follows, that the disclosed Group V-containing film forming compositions are suitable for atomic layer deposition (ALD). More particularly, the disclosed Group V- containing film forming compositions are capable of surface saturation, self limited growth per cycle, and perfect step coverage on aspect ratios ranging from approximately 2:1 to approximately 200:1 , and preferably from approximately 20:1 to approximately 100:1. Additionally, the disclosed Group V-containing film forming compositions have high decomposition temperatures, indicating good thermal stability to enable ALD. The high decomposition temperatures permit ALD at higher temperatures, resulting in films having higher purity.
[0055] The disclosed method may be useful in the manufacture of semiconductor, photovoltaic, LCD-TFT, flat panel type devices. The disclosed Group V-containing film
forming compositions may be used to deposit Group V-containing films using any deposition methods known to those of skill in the art. Examples of suitable vapor deposition methods include chemical vapor deposition (CVD) atomic layer deposition (ALD). Exemplary CVD methods include thermal CVD, plasma enhanced CVD (PECVD), pulsed CVD (PCVD), low pressure CVD (LPCVD), sub-atmospheric CVD (SACVD) atmospheric pressure CVD (APCVD), hot-wire CVD (HWCVD, also known as cat-CVD, in which a hot wire serves as an energy source for the deposition process), radicals incorporated CVD, and combinations thereof. Exemplary ALD methods include thermal ALD, plasma enhanced ALD (PEALD), spatial ALD, hot-wire ALD (HWALD), radicals incorporated ALD, and combinations thereof, Super critical fluid deposition may also be used. The deposition method is preferably ALD, PE-ALD, spatial ALD in order to provide suitable step coverage and film thickness control, [0056] The disclosed Group V-containing film forming compositions may be supplied either in neat form in a blend with a suitable solvent, such as ethyl benzene, xylene, mesitylene, decalin, decane, dodecane. The disclosed precursors may be present in varying concentrations in the solvent.
[0057] The neat blended Group V-containing film forming compositions are introduced into a reactor in vapor form by conventional means, such as tubing and/or flow meters. The vapor form may be produced by vaporizing the neat blended composition through a conventional vaporization step such as direct vaporization, distillation, by bubbling, or by using a sublimator. The neat blended composition may be fed in liquid state to a vaporizer where it is vaporized before it is introduced into the reactor. Alternatively, the neat blended composition may be vaporized by passing a carrier gas into a container containing the composition by bubbling the carrier gas into the composition. The carrier gas may include, but is not limited to, Ar, He, N2, and mixtures thereof. Bubbling with a carrier gas may also remove any dissolved oxygen present in the neat blended composition. The carrier gas and composition are then introduced into the reactor as a vapor,
[0058] If necessary, the container containing the disclosed Group V-containing film forming composition may be heated to a temperature that permits the composition to be in its liquid phase and to have a sufficient vapor pressure. The container may be maintained at temperatures in the range of, for example, approximately 0°C to approximately 200°C. Those skilled in the art recognize that the temperature of the container may be adjusted in a known manner to control the amount of precursor vaporized.
[0059] The reactor may be any enclosure chamber within a device in which deposition methods take place such as without limitation, a parallel-plate type reactor, a cold-wall type reactor, a hot-wall type reactor, a single-wafer reactor, a multi-wafer reactor, a powder ALD
reactor, other types of deposition systems under conditions suitable to cause the compounds to react and form the layers. One of ordinary skill in the art will recognize that any of these reactors may be used for either ALD or CVD deposition processes.
[0060] The reactor contains one more substrates onto which the films will be deposited. A substrate is generally defined as the material on which a process is conducted. The substrates may be any suitable substrate used in semiconductor, photovoltaic, fiat panel, LCD-TFT device manufacturing. Examples of suitable substrates include wafers, such as silicon, silica, glass, GaAs wafers. The wafer may have one more layers of differing materials deposited on it from a previous manufacturing step. For example, the wafers may include a dielectric layer. Furthermore, the wafers may include silicon layers (crystalline, amorphous, porous, etc,), silicon oxide layers, silicon nitride layers, silicon oxy nitride layers, carbon doped silicon oxide (SiCOH) layers, metal, metal oxide, metal nitride layers (Ti, Ru, Ta, etc,) combinations thereof. Additionally, the wafers may include copper layers noble metal layers (e.g., platinum, palladium, rhodium, and gold). Plastic layers, such as poly(3,4- ethylenedioxythiophene)poly(styrenesulfonate)[PEDOT:PSS] may also be used. The layers may be planar or patterned. The disclosed processes may deposit the Group V-containing layer directly on the wafer or directly on one or more layers on top of the wafer (when patterned layers form the substrate). Furthermore, one of ordinary skill in the art will recognize that the terms “film” “layer” used herein refer to a thickness of some material laid on spread over a surface and that the surface may be a trench a line. Throughout the specification and claims, the wafer and any associated layers thereon are referred to as substrates. For example, a Niobium oxide film may be deposited onto a metal oxide layer, such as a ZrO2 layer, an HfO2 layer, an AI2O3 layer, a MoOs layer. In subsequent processing, another metal oxide layer may be deposited on the Niobium oxide layer to form a nanolaminate; for example, ZrO2/Nb2O/ZrO2 laminate dielectric stack are typical of DRAM high-k stack. A conductive metal nitride layer, such as a Niobium Nitride layer or a Titanium Nitride layer, may be deposited before on the last metal oxide layer to form, respectively, the bottom and top electrodes. The resulting NbN/ZrO2/Nb2O/ZrO2/NbN stack may be used in DRAM capacitors. Other conductive films, such as RuO, Ru, Pt, Ir, WN, WNC, may be also used as the bottom top electrodes, alone in addition to the NbN or TaN layers.
[0061] The substrate may also be a powder, such as the powder used in rechargeable battery technology. A non-limiting number of powder materials include NMC (Lithium Nickel Manganese Cobalt Oxide), LCO (Lithium Cobalt Oxide), LFP (Lithium Iron Phosphate), and other battery cathode materials.
[0062] The temperature and the pressure within the reactor are held at conditions suitable
for ALD. In other words, after introduction of the vaporized disclosed composition into the chamber, conditions within the chamber are such that at least part of the precursor is deposited onto the substrate to form a Group V (five)-containing layer. For instance, the pressure in the reactor or the deposition pressure may be held between about 10-3 torr and about 100 Torr, more preferably between about 10-2 and 100 Torr, as required per the deposition parameters. Likewise, the temperature in the reactor or the deposition temperature may be held between about 100°C and about 600°C, preferably between about 150°C and about 500°C. One of ordinary skill in the art will recognize that “at least part of the precursor is deposited” means that some all of the precursor reacts with adheres to the substrate.
[0063] The temperature of the reactor may be controlled by either controlling the temperature of the substrate holder controlling the temperature of the reactor wall. Devices used to heat the substrate are known in the art. The reactor wall is heated to a sufficient temperature to obtain the desired film at a sufficient growth rate and with desired physical state and composition. A non-limiting exemplary temperature range to which the reactor wall may be heated includes from approximately 50°C to approximately 600°C. When a plasma deposition process is utilized, the deposition temperature may range from approximately 50°C to approximately 500°C, preferably, from approximately 100°C to approximately 500°C1 more preferably, from approximately 150°C to approximately 500°C. Alternatively, when a thermal process is performed, the deposition temperature may range from approximately 10CTC to approximately 600° C.
[0064] In addition to the disclosed Group V-containing film forming composition, a coreactant may be introduced into the reactor. When the target is a conductive film, the coreactant may be H2, H2CO, N2H4, NH3, a primary amine, a secondary amine, a tertiary amine, trisilylamine, a hydrazine N(SiH3)3, B2H66 Si2H6, radicals thereof, and mixtures thereof. Preferably, the co-reactant is H2/NH3.
[006S] Alternatively, when the target is a dielectric film, the co-reactant may be an oxidizing gas such as one of O2, O3, H2O, H2O2, NO, N2O, NO2, oxygen containing radicals such as O- OH-, carboxylic acids, formic acid, acetic acid, propionic acid, and mixtures thereof. Preferably, the oxidizing gas is selected from the group consisting of O3, H2O2 H2O. [0066] The co-reactant may be treated by a plasma, in order to decompose the reactant into its radical form, N2 may also be utilized as a nitrogen source gas when treated with plasma. For instance, the plasma may be generated with a power ranging from about 10 W to about 1000 W, preferably from about 50 W to about 500 W. The plasma may be generated present within the reactor itself. Alternatively, the plasma may generally be at a location
removed from the reactor, for instance, in a remoteiy iocated plasma system. One of skill in the art will recognize methods and apparatus suitable for such plasma treatment.
[0067] For example, the co-reactant may be introduced into a direct plasma reactor, which generates plasma in the reaction chamber, to produce the plasma-treated reactant in the reaction chamber. Exemplary direct plasma reactors include the Titan™ PECVD System produced by Trion Technologies. The co-reactant may be introduced and held in the reaction chamber prior to plasma processing. Alternatively, the plasma processing may occur simultaneously with the introduction of the reactant. In-situ plasma is typically a 13.56 MHz RF inductively coupled plasma that is generated between the showerhead and the substrate holder. The substrate the showerhead may be the powered electrode depending on whether positive ion impact occurs. Typical applied powers In in-situ plasma generators are from approximately 30 Wto approximately 1000 W. Preferably, powers from approximately 30 W to approximately 600 W are used in the disclosed methods. More preferably, the powers range from approximately 100 W to approximately 500 W. The disassociation of the coreactant using in-situ plasma is typically less than achieved using a remote plasma source for the same power input and is therefore not as efficient in reactant dissociation as a remote plasma system, which may be beneficial for the deposition of Group V (five)-containing films on substrates easily damaged by plasma.
[0068] Alternatively, the plasma-treated co-reactant may be produced outside of the reaction chamber, for example, a remote plasma to treat the co-reactant prior to passage into the reaction chamber.
[0069] The ALD conditions within the chamber allow the disclosed Group V-containing film forming composition adsorbed chemisorbed on the substrate surface to react and form a Group V-containing film on the substrate. In some embodiments, Applicants believe that plasma-treating the co-reactant may provide the co-reactant with the energy needed to react with the disclosed Group V-containing film forming composition.
[0070] Depending on what type of film is desired to be deposited, an additional precursor compound may be introduced Into the reactor. The additional precursor may be used to provide additional elements to the Group V-containing film. The additional elements may include Group I elements (lithium, Sodium, potassium), lanthanides (Ytterbium, Erbium, Dysprosium, Gadolinium, Praseodymium, Cerium, Lanthanum, Yttrium), Group IV elements (zirconium, titanium, hafnium), main group elements (germanium, silicon, aluminium), additional different Group V elements, and mixtures thereof. When an additional precursor compound is utilized, the resultant film deposited on the substrate contains the Group V metal in combination with an additional element. When the additional precursor and the Group V
precursors are used in more than one ALD super cycle sequences, a nanolaminate film is obtained. For instance, when an additional Li-containing precursor is used, the Group V- containing film will contain Li, such as, a lithium noibiate (LiNbO3) film. One of ordinary skilled in the art will recognize the Group V-containing films containing Li may be formed by ALD on any types of substrates including a powder.
[0071] The Group V-containing film forming composition and co-reactants may be introduced into the reactor sequentially (i.e. , ALD). The reactor may be purged with an inert gas (e.g., N2, He, Ar, Kr, or Xe ) between the introduction of each of the Group V-containing film forming composition, any additional precursors, and the co-reactants. Another example is to introduce the co-reactant continuously and to introduce the Group V-containing film forming composition by pulse, while activating the co-reactant sequentially with a plasma, provided that the Group V-containing film forming composition and the non-activated co- reactant do not substantially react at the chamber temperature and pressure conditions (CW PEALD).
[0072] Each pulse of the disclosed Group V-containing film forming composition may last for a time period ranging from about 0.01 seconds to about 120 seconds, alternatively from about 1 seconds to about 80 seconds, alternatively from about 5 seconds to about 30 seconds. The co-reactant may also be pulsed into the reactor, in such embodiments, the pulse of each may last for a time period ranging from about 0.01 seconds to about 120 seconds, alternatively from about 1 seconds to about 30 seconds, alternatively from about 2 seconds to about 20 seconds. In another alternative, the vaporized Group V-containing film forming compositions and co-reactants may be simultaneously sprayed from different sectors of a shower head (without mixing of the composition and the reactant) under which a susceptor holding several wafers is spun (spatial ALD).
[0073] Depending on the particular process parameters, deposition may take place for a varying length of time. Generally, deposition may be allowed to continue as long as desired necessary to produce a film with the necessary properties. Typical film thicknesses may vary from several angstroms to several hundreds of microns, and typically from 2 to 100 nm, depending on the specific deposition process. The deposition process may also be performed as many times as necessary to obtain the desired film.
[0074] In one non-limiting exemplary ALD process, the vapor phase of the disclosed Group V-containing film forming composition is introduced into the reactor, where it is contacted with a suitable substrate. Excess composition may then be removed from the reactor by purging and/or evacuating the reactor. A co-reactant (for example, O3) is introduced into the reactor where it reacts with the absorbed Group V-containing film forming
composition in a self-limiting manner. Any excess co-reactant is removed from the reactor by purging and/or evacuating the reactor. If the desired film is a Group V-containing oxide, this two-step process may provide the desired film thickness may be repeated until a film having the necessary thickness has been obtained.
[0075] Alternatively, if the desired film contains the Group V (five) transition metal and a second element, such as Li, the two-step process above may be followed by introduction of the vapor of an additional precursor compound into the reactor. The additional precursor compound will be selected based on the nature of the Group V-containing film being deposited. After introduction into the reactor, the additional precursor compound is contacted with the substrate. Any excess precursor compound is removed from the reactor by purging and/or evacuating the reactor. Once again, a co-reactant may be introduced into the reactor to react with the precursor compound. Excess co-reactant is removed from the reactor by purging and/or evacuating the reactor. If a desired film thickness has been achieved, the process may be terminated. However, if a thicker film is desired, the entire four-step process may be repeated. By alternating the provision of the Group V-containing film forming composition, additional precursor compound, and co-reactant, a film of desired composition and thickness can be deposited. In one non-limiting exemplary ALD process, the vapor phase of one of the disclosed Group V-containing film forming composition, for example, Niobium tButyl Imido Cyclopentadienyl tAmyl-Diazadienyl, CpNb(= NtBu)(tAm2-DAD, is introduced into the reactor, where it is contacted with a powder substrate and absorbed thereon. Excess composition may then be removed from the reactor by purging and/or evacuating the reactor. A co-reactant (for example, O3) is introduced into the reactor where it reacts with the absorbed CpNb(=NtBu)(tAm2-DAD in a self-limiting manner to form a Nb oxide film. Any excess O3 gas is removed from the reactor by purging and/or evacuating the reactor. A Li- containing precursor may then be exposed to the powder substrate and/or the Nb oxide film to form a Li and Nb oxide film LiNbO3. For example, LiOtBu, may serve as the Li precursor. This non-limiting exemplary ALD process described above using CpNb(=NtBu)(tAm2-DAD, O3 and LiOtBu may then be repeated on the powder until a desired thickness of the LiNbO3 film depoaited on the powder. The resulting LINbOs film may be used in rechargeable battery applications. One of ordinary skilled in the art will recognize that the suitable lithium precursors include, but are not limited to, LiOtBu, LiN(Si R3)2 wherein each R is selected from H, a C1 to C4 alkyl or alkeny group, Li(DPM) (lithium dipivaloylmethane aka lithium 2, 2,6,6- tetramethyl-3,5-heptanedionate) or any other suitable lithium ALD precursors.
[0076] When the co-reactant in this exemplary ALD process is treated with a plasma, the exemplary ALD process becomes an exemplary PEALD process. The co-reactant may be
treated with plasma prior subsequent to introduction into the chamber.
[0077] In a second non-limiting exemplary ALD process, the vapor phase of one of the disclosed Group V-containing film forming composition, for example Niobium tButyl Imido Cyclopentadienyl tAmyl-Diazadienyl, CpNb(=NtBu)(tAm2-DAD), is introduced into the reactor, where it is contacted with a Si substrate. Excess composition may then be removed from the reactor by purging and/or evacuating the reactor. A co-reactant (for example, O3) is introduced into the reactor where it reacts with the absorbed Group V-containing film forming composition in a self-limiting manner to form a Group V-containing oxide film. Any excess O3 gas is removed from the reactor by purging and/or evacuating the reactor. These two steps may be repeated until the Group V-containing oxide film obtains a desired thickness, typically around 10 angstroms, ZrO2 may then be deposited on the Group V-containing oxide film, For example, ZrCp(NMe2)3 or HfCp(NMe2)3 may serve as the Zr or Hf precursor repectively. The second non-limiting exemplary ALD process described above using CpNb(=NtBu)(tAm2- DAD) and O3 may then be repeated on the ZrO2 or HfO2 layer. The resultingNb2O5/ZrO2/Nb2O5, Nb2O5/HfO2/Nb2O5 or Nb2O5/HZO/Nb2O5 stack may be used in DRAM capacitors. Here HZO represents Hafnium Zirconium Oxide.
[0078] In another exemplary ALD process, another precursor may be introduced sequentially between one several ALD super-cycles (e.g., O-containing co-reactant/ Group V-containing precursor/O-containing co-reactant) in order to deposit a Group V-containing MO film an Group V (five)-containing O/MO nanolaminate, M being selected from a Group IV element a different group V (five) element, silicon, germanium, aluminium, or any lanthanide. The M precursor selected preferably undergoes ALD growth in the same temperature window exhibited by the selected Group V-containing film forming composition. [0079] The Group V-containing films resulting from the processes discussed above may include Nb, NbkSii, NbnOm, Nb0Np, NboNpOq, wherein k, I, m, n, 0, p, and q may each independently range from 1 to 6. Exemplary films include NbO2, Nb2O5, NbN, and NbON, One of ordinary skill in the art will recognize that by appropriate selection of the Group V- containing film forming composition co-reactants, the desired film composition may be obtained. The Group V-containing films may provide suitable step coverage for capacitor electrodes in DRAM, the gate metal in 3D Flash memory devices, the heating element in phase change memory, the electromigration barrier layer, gate metal, and contact layers in logic devices.
[0080] Upon obtaining a desired film thickness, the film may be subject to further processing, such as thermal annealing, furnace-annealing, rapid thermal annealing, UV e- beam curing, and microwave annealing and/or plasma gas exposure. Those skilled in the art
recognize the systems and methods utilized to perform these additional processing steps. For example, the Nb2O5 film may be exposed to a temperature ranging from approximately 200°C and approximately 1000°C for a time ranging from approximately 0.1 second to approximately 7200 seconds under an inert atmosphere, an O-containing atmosphere, H~ containing atmosphere combinations thereof. Most preferably, the temperature is 400°C for 3600 seconds under an inert atmosphere or an O-containing atmosphere. The resulting film may contain fewer impurities and therefore may have an improved density resulting in improved leakage current. The annealing step may be performed in the same reaction chamber in which the deposition process is performed. Alternatively, the substrate may be removed from the reaction chamber, with the annealing/flash annealing process being performed in a separate apparatus. Any of the above post-treatment methods, but especially thermal annealing, has been found effective to reduce carbon and nitrogen contamination of the Nb2O5 film. This in turn tends to improve the resistivity of the film.
[0081] After annealing, the Group V-containing films deposited by any of the disclosed processes may have a bulk resistivity at room temperature of approximately 50 pohm-cm to approximately 1 ,000 pohm-cm. Room temperature is approximately 20°C to approximately 28°C depending on the season. Bulk resistivity is also known as volume resistivity. One of ordinary skill in the art will recognize that the bulk resistivity is measured at room temperature on the Group V-containing films that are typically approximately 50 nm thick. The bulk resistivity typically increases for thinner films due to changes in the electron transport mechanism. The bulk resistivity also increases at higher temperatures.
[0082] In another alternative, the disclosed compositions may be used as doping implantation agents. Part of the disclosed Group V-containing film forming composition may be deposited on top of the film to be doped, such as an indium oxide (ln2O3) film, tantalum dioxide (TaO2), vanadium dioxide (VO2) film, a titanium oxide film, a copper oxide film, or a tin dioxide (SnO2) film. The Group V (five) element, for example Nb, then diffuses into the film during an annealing step to form the Group V (five) element-doped films, such as {(Nb)ln2O3, (Nb)VO2, (Nb)TiO, (Nb)CuO, (Nb)SnO2}. See, e.g., US2008/0241575 to Lavoie et al., the doping method of which is incorporated herein by reference in its entirety.
Examples
[0083] The following non-limiting examples are provided to further illustrate embodiments of the invention. However, the examples are not intended to be all inclusive and are not intended to limit the scope of the inventions described herein.
Example 1. Synthesis of Niobium tButyl Imido Cyclopentadienyl tAmyl-Diazadienyl, CpNb(=NtBu)(tAm2-DAD)
[0084] A solution of Sodium Cyclopentadienyl (2.4 mL. 2.0 M, 4.8 mmol) was added dropwise to a solution of Nb(=NtBu)Ch(py)2 (2 g, 4.6 mmol) in 30 mL of THF at -78°C to form a mixture. The mixture was stirred under room temperature for 12 h. The color of the mixture turned to yellow. A fresh red solution of lithium tAmyl-Diazadienyl in THF, prepared from the reaction of tAmyl-Diazadiene (0.9 g, 4.6 mmol) and pure Lithium (80 mg, 11.5 mmol), was then added to the mixture at -78°C. Afterwards the color of the mixture turned to dark brown. After stirring overnight under room temperature, the solvent was removed from the mixture under vacuum and a brown oil product was extracted with pentane. The brown oil product was then purified by distillation up to 220°C @ 25 mTorr to give 0.23 g (11 %) of brown oil. The purified product was characterized by NMR 1H (δ, ppm, C6D6): 5.68 (s, 5H), 5.65 (s, 2H), 1.60 (m, 4H), 1.29 (s, 6H), 1.26(s, 9H), 1.14 (s, 6H), 0.79(t, 6H).
[0085] The purified product left a 1.2% residual mass during open-cup TGA analysis measured at a temperature rising rate of 10'C/min in an inert atmosphere that flows nitrogen at 200 mL/min. The results are shown in FIG. 1, which is a TGA graph illustrating the percentage of weight loss upon temperature increase. Onset temperature of melting (26°C) and decomposition (422“C) of the product were measured by differential scanning calorimetry (DSC), which are shown in FIG. 2.
Example 2. ALD results of Niobium tButyl Imido Cyclopentadienyl tAmyl-Diazadienyl, CpNb(=NtBu)(tAm2-DAD)
[0086] CpNb(=NtBu)(tAm2-DAD) was stored in a container. The container was heated at 90°C, and Ar was used as a carrier gas to carry CpNb(=NtBu)(tAm2-DAD) into a reactor at a flow of 200 sccm. O3 was used as oxygen source. The substrate was heated from 200 to 400°C. During a first step, CpNb(=NtBu)(tAm2-DAD) (with the carrier gas Ar) was introduced into the reaction chamber in 10s. An Ar purge of 10s was performed afterwards as second step. As third step, a pulse of O3, was then introduced into the reaction chamber in 1s,
an Nb2O5fiim. Self-limited atomic layer deposition was obtained.
[0087] FIG, 3, FIGs 4a to 4c and FIG, 5 are the ALD results of CpNb(=NtBu)(tAm2-DAD). The growth rate was 0.3A per cycle and the ALD window was up to 325°C (FIG. 3). FIG. 4a showed a full image of excellent step coverage in 1 :15 aspect ratio patterned wafer at 325°C by SEM. FIG, 4b showed top image of FIG. 4a and FIG. 4c showed bottom image of FIG. 4a. FIG. 5 is an XPS depth profile that shows proper composition ratio of Nb2O5 and negligible Impurity level at 325°C.
[0088] Although the subject matter described herein may be described in the context of illustrative implementations to process one or more computing application features/operations for a computing application having user-interactive components the subject matter is not limited to these particular embodiments. Rather, the techniques described herein may be applied to any suitable type of user-interactive component execution management methods, systems, platforms, and/or apparatus.
[0089] It will be understood that many additional changes in the details, materials, steps, and arrangement of parts, which have been herein described and illustrated in order to explain the nature of the invention, may be made by those skilled in the art within the principle and scope of the invention as expressed in the appended claims. Thus, the present invention is not intended to be limited to the specific embodiments in the examples given above and/or the attached drawings.
[0090] While embodiments of this invention have been shown and described, modifications thereof may be made by one skilled in the art without departing from the spirit or teaching of this invention. The embodiments described herein are exemplary only and not limiting. Many variations and modifications of the composition and method are possible and within the scope of the invention. Accordingly, the scope of protection is not limited to the embodiments described herein, but Is only limited by the claims which follow, the scope of which shall include ail equivalents of the subject matter of the claims.
Claims
1 . A method for forming a Group V (five)-containing film, the method comprising the steps of: a) exposing a substrate to a vapor of a Group V (five)-containing film forming composition; b) exposing the substrate to a co-reactant; and c) repeating the steps of a) and b) until a desired thickness of the Group V (five)-containing film is deposited on the substrate using a vapor deposition process, wherein the Group V (five)-containing film forming composition comprises a precursor having the formula:
wherein M is Group V (five) element, vanadium (V), niobium (Nb), or tantalum (Ta);
R1 to R8 each is H, a C1-C6 alkyl group, a fluoro group, an alkylsilyl group, a germyl group, an aikyiamide or an alkylsilylamide; m = 1 to 5, n = 1 to 5.
2. The method of claim 1 , further comprising the step of introducing an inert gas purge following the steps a) and b), respectively, to separate each exposure, wherein the inert gas purge uses an inert gas selected from N2, He, Ar, Kr, or Xe.
3. The method of claim 1 , further comprising the step of plasma treating the co- reactant.
4. The method of any one of ciaims 1 to 3, wherein the co-reactant is selected from the group consisting of O2, O3, H2O, H2O2, NO, N2O, NO2, oxygen radicals thereof, and mixtures thereof.
5. The method of any one of claims 1 to 3, wherein the co-reactant is selected from the group consisting of H2, H2CO, N2H4, NH3, an amine, a hydrazine N(SiH3)3, B2H6, Si2H6 radicals thereof, and mixtures thereof.
6 The method of any one of ciaims 1 to 3, wherein the precursor includes
7. The method of any one of claims 1 to 3, wherein the precursor is Niobium tButy I Imido Cyciopentadienyi tAmyl-Diazadienyl, CpNb(=NtBu)(tAm2-DAD).
8. The method of any one of claims 1 to 3, wherein a deposition temperature ranges from approximately 50°C and approximately 600°C.
9. A Group V (five)-containing film forming composition for a vapor deposition process comprising a precursor having the formula:
wherein M is Group V (five) element, vanadium (V), niobium (Nb), or tantalum (Ta);
R1 to R8 each is H, a Ci-Ce alkyl group, a fluoro group, an alkylsilyl group, a germyl group, an alkylamide or an alkylsilylamide; m = 1 to 5, n = 1 to 5.
10. The Group V (five)-containing film forming composition of claim 9, wherein the precursor includes (R3R4R5R6R7Cp)Nb(=NR1)(R2 2-DAD),
and (R3R4R5R6R7Cp)Nb(=NR1)(R2 2-EDA),
wherein DAD = Diazadiene; EDA is Ethylenediamine; R1 is tBu or nPr ; R2 is Me, Et, nPr, IPr, nBu, tBu, nPentyl or tAm; R3, R4, R5, R6 and R7 each is Independently H, Me, Et, nPr, IPr, nBu, tBu or sBu.
11. The Group V (five)-containing film forming composition of claim 9, wherein the precursor is Niobium tButyl Imido Cyclopentadienyl tAmyl-Diazadienyl, CpNb(=NtBu)(tAm2- DAD).
12. A method of forming an Nb2O5 film or coating by an ALD process on a substrate, the method comprising the steps of: a) exposing the substrate to a vapor of Niobium tButyl Imido Cyclopentadienyl tAmyl-Diazadienyl (CpNb(=NtBu)(tAm2-DAD)); b) exposing the substrate to an oxidizer; and c) repeating the steps of a) and b) until a desired thickness of the Nb2O5 film is deposited on the substrate using the ALD process.
13. The method of claim 12, further comprising the steps of introducing an inert gas purge following the steps a) and b), respectively, to separate each exposure.
14. The method of claim 12, wherein the substrate is a powder.
15. The method of any one of claims 12 to 14, wherein the powder comprises one or more of NMC (Lithium Nickel Manganese Cobalt Oxide), LCO (Lithium Cobalt Oxide), LFP (Lithium Iron Phosphate), and other battery cathode materials.
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Citations (3)
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JP2007031431A (en) * | 2005-07-15 | 2007-02-08 | Hc Starck Gmbh | Tantalum and niobium compound and their use for chemical vapor deposition (cvd) process |
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