US20080254218A1 - Metal Precursor Solutions For Chemical Vapor Deposition - Google Patents
Metal Precursor Solutions For Chemical Vapor Deposition Download PDFInfo
- Publication number
- US20080254218A1 US20080254218A1 US12/058,200 US5820008A US2008254218A1 US 20080254218 A1 US20080254218 A1 US 20080254218A1 US 5820008 A US5820008 A US 5820008A US 2008254218 A1 US2008254218 A1 US 2008254218A1
- Authority
- US
- United States
- Prior art keywords
- metal
- alkyl
- group
- linear
- branched
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 187
- 239000002184 metal Substances 0.000 title claims abstract description 185
- 239000002243 precursor Substances 0.000 title claims abstract description 58
- 238000005229 chemical vapour deposition Methods 0.000 title claims abstract description 20
- 125000003118 aryl group Chemical group 0.000 claims abstract description 36
- 239000003446 ligand Substances 0.000 claims abstract description 29
- 150000004696 coordination complex Chemical class 0.000 claims abstract description 19
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 16
- 230000008569 process Effects 0.000 claims abstract description 15
- 238000000231 atomic layer deposition Methods 0.000 claims abstract description 13
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 239000000758 substrate Substances 0.000 claims abstract description 7
- 150000001408 amides Chemical class 0.000 claims abstract description 6
- 150000003857 carboxamides Chemical class 0.000 claims abstract description 6
- 150000004703 alkoxides Chemical class 0.000 claims abstract description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 97
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 64
- 125000003342 alkenyl group Chemical group 0.000 claims description 33
- 125000000304 alkynyl group Chemical group 0.000 claims description 33
- 125000004122 cyclic group Chemical group 0.000 claims description 31
- 125000005103 alkyl silyl group Chemical group 0.000 claims description 27
- 239000010949 copper Substances 0.000 claims description 27
- 239000001257 hydrogen Substances 0.000 claims description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims description 21
- 150000002739 metals Chemical class 0.000 claims description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 15
- 229910052707 ruthenium Inorganic materials 0.000 claims description 14
- 229910052802 copper Inorganic materials 0.000 claims description 13
- 229910052712 strontium Inorganic materials 0.000 claims description 13
- 229910052746 lanthanum Inorganic materials 0.000 claims description 12
- 229910052741 iridium Inorganic materials 0.000 claims description 11
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- 229910052703 rhodium Inorganic materials 0.000 claims description 11
- 239000010948 rhodium Substances 0.000 claims description 11
- 229910052788 barium Inorganic materials 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 9
- 239000010936 titanium Substances 0.000 claims description 9
- 229910052684 Cerium Inorganic materials 0.000 claims description 8
- 229910052691 Erbium Inorganic materials 0.000 claims description 8
- 229910052772 Samarium Inorganic materials 0.000 claims description 8
- 229910052771 Terbium Inorganic materials 0.000 claims description 8
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 229910052791 calcium Inorganic materials 0.000 claims description 8
- 229910052735 hafnium Inorganic materials 0.000 claims description 8
- 229910052745 lead Inorganic materials 0.000 claims description 8
- 229910052749 magnesium Inorganic materials 0.000 claims description 8
- 229910021645 metal ion Inorganic materials 0.000 claims description 8
- 229910052727 yttrium Inorganic materials 0.000 claims description 8
- WSNDAYQNZRJGMJ-UHFFFAOYSA-N 2,2,2-trifluoroethanone Chemical compound FC(F)(F)[C]=O WSNDAYQNZRJGMJ-UHFFFAOYSA-N 0.000 claims description 7
- GOVWJRDDHRBJRW-UHFFFAOYSA-N diethylazanide;zirconium(4+) Chemical compound [Zr+4].CC[N-]CC.CC[N-]CC.CC[N-]CC.CC[N-]CC GOVWJRDDHRBJRW-UHFFFAOYSA-N 0.000 claims description 7
- ZYLGGWPMIDHSEZ-UHFFFAOYSA-N dimethylazanide;hafnium(4+) Chemical compound [Hf+4].C[N-]C.C[N-]C.C[N-]C.C[N-]C ZYLGGWPMIDHSEZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 229910052726 zirconium Inorganic materials 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 4
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 claims description 4
- 239000004912 1,5-cyclooctadiene Substances 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 230000003412 degenerative effect Effects 0.000 claims description 4
- VBCSQFQVDXIOJL-UHFFFAOYSA-N diethylazanide;hafnium(4+) Chemical compound [Hf+4].CC[N-]CC.CC[N-]CC.CC[N-]CC.CC[N-]CC VBCSQFQVDXIOJL-UHFFFAOYSA-N 0.000 claims description 4
- VJDVOZLYDLHLSM-UHFFFAOYSA-N diethylazanide;titanium(4+) Chemical compound [Ti+4].CC[N-]CC.CC[N-]CC.CC[N-]CC.CC[N-]CC VJDVOZLYDLHLSM-UHFFFAOYSA-N 0.000 claims description 4
- DWCMDRNGBIZOQL-UHFFFAOYSA-N dimethylazanide;zirconium(4+) Chemical compound [Zr+4].C[N-]C.C[N-]C.C[N-]C.C[N-]C DWCMDRNGBIZOQL-UHFFFAOYSA-N 0.000 claims description 4
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- PZYDAVFRVJXFHS-UHFFFAOYSA-N n-cyclohexyl-2-pyrrolidone Chemical compound O=C1CCCN1C1CCCCC1 PZYDAVFRVJXFHS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Chemical group 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- YAYGSLOSTXKUBW-UHFFFAOYSA-N ruthenium(2+) Chemical compound [Ru+2] YAYGSLOSTXKUBW-UHFFFAOYSA-N 0.000 claims description 4
- MNWRORMXBIWXCI-UHFFFAOYSA-N tetrakis(dimethylamido)titanium Chemical compound CN(C)[Ti](N(C)C)(N(C)C)N(C)C MNWRORMXBIWXCI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 239000010955 niobium Substances 0.000 claims description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000007740 vapor deposition Methods 0.000 claims description 3
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 2
- 125000000041 C6-C10 aryl group Chemical group 0.000 claims description 2
- JVCWKXBYGCJHDF-UHFFFAOYSA-N CC(C)(C)N=[W](N(C)C)(=NC(C)(C)C)N(C)C Chemical compound CC(C)(C)N=[W](N(C)C)(=NC(C)(C)C)N(C)C JVCWKXBYGCJHDF-UHFFFAOYSA-N 0.000 claims description 2
- QQBINNXWRDRCHB-UHFFFAOYSA-N CCC(C)(C)N=[Ta](N(C)C)(N(C)C)N(C)C Chemical compound CCC(C)(C)N=[Ta](N(C)C)(N(C)C)N(C)C QQBINNXWRDRCHB-UHFFFAOYSA-N 0.000 claims description 2
- DBRFWHCIZLNDBF-UHFFFAOYSA-N CCC[Hf](CCC)(CCC)CCC Chemical compound CCC[Hf](CCC)(CCC)CCC DBRFWHCIZLNDBF-UHFFFAOYSA-N 0.000 claims description 2
- LXGVSTJKGLJWEQ-UHFFFAOYSA-N CCC[Ti](CCC)(CCC)CCC Chemical compound CCC[Ti](CCC)(CCC)CCC LXGVSTJKGLJWEQ-UHFFFAOYSA-N 0.000 claims description 2
- DDRHFMPLKPRDPQ-UHFFFAOYSA-N CCC[Zr](CCC)(CCC)CCC Chemical compound CCC[Zr](CCC)(CCC)CCC DDRHFMPLKPRDPQ-UHFFFAOYSA-N 0.000 claims description 2
- PDGHBHKZHSFTHO-UHFFFAOYSA-N CCN(C)[Ta](=NC(C)(C)C)(N(C)CC)N(C)CC Chemical compound CCN(C)[Ta](=NC(C)(C)C)(N(C)CC)N(C)CC PDGHBHKZHSFTHO-UHFFFAOYSA-N 0.000 claims description 2
- GKBKXJWUIIYCBD-UHFFFAOYSA-N CCN(C)[Ta](N(C)CC)(N(C)CC)=NC(C)(C)CC Chemical compound CCN(C)[Ta](N(C)CC)(N(C)CC)=NC(C)(C)CC GKBKXJWUIIYCBD-UHFFFAOYSA-N 0.000 claims description 2
- WBDYMROSBUOORV-UHFFFAOYSA-N CCN(C)[Ta](N(C)CC)N(C)CC Chemical compound CCN(C)[Ta](N(C)CC)N(C)CC WBDYMROSBUOORV-UHFFFAOYSA-N 0.000 claims description 2
- KKSXSQXELVXONV-UHFFFAOYSA-N CCN(C)[W](=NC(C)(C)C)(=NC(C)(C)C)N(C)CC Chemical compound CCN(C)[W](=NC(C)(C)C)(=NC(C)(C)C)N(C)CC KKSXSQXELVXONV-UHFFFAOYSA-N 0.000 claims description 2
- YYKBKTFUORICGA-UHFFFAOYSA-N CCN(CC)[Ta](=NC(C)(C)C)(N(CC)CC)N(CC)CC Chemical compound CCN(CC)[Ta](=NC(C)(C)C)(N(CC)CC)N(CC)CC YYKBKTFUORICGA-UHFFFAOYSA-N 0.000 claims description 2
- GODRSDDUYGEYDK-UHFFFAOYSA-N CCN(CC)[Ta](N(CC)CC)(N(CC)CC)=NC(C)(C)CC Chemical compound CCN(CC)[Ta](N(CC)CC)(N(CC)CC)=NC(C)(C)CC GODRSDDUYGEYDK-UHFFFAOYSA-N 0.000 claims description 2
- YZHQWZURESVKOE-UHFFFAOYSA-N CCN(CC)[Ta](N(CC)CC)N(CC)CC Chemical compound CCN(CC)[Ta](N(CC)CC)N(CC)CC YZHQWZURESVKOE-UHFFFAOYSA-N 0.000 claims description 2
- IVBDGJZEAHBGFJ-UHFFFAOYSA-N CCN(CC)[W](=NC(C)(C)C)(=NC(C)(C)C)N(CC)CC Chemical compound CCN(CC)[W](=NC(C)(C)C)(=NC(C)(C)C)N(CC)CC IVBDGJZEAHBGFJ-UHFFFAOYSA-N 0.000 claims description 2
- FBNHWOBJTUBDME-UHFFFAOYSA-N CN(C)[Ta](N(C)C)(N(C)C)=NC(C)(C)C Chemical compound CN(C)[Ta](N(C)C)(N(C)C)=NC(C)(C)C FBNHWOBJTUBDME-UHFFFAOYSA-N 0.000 claims description 2
- IYZDEOSFLDNSDK-UHFFFAOYSA-N CN(C)[Ta](N(C)C)N(C)C Chemical compound CN(C)[Ta](N(C)C)N(C)C IYZDEOSFLDNSDK-UHFFFAOYSA-N 0.000 claims description 2
- 229910017333 Mo(CO)6 Inorganic materials 0.000 claims description 2
- 229910008940 W(CO)6 Inorganic materials 0.000 claims description 2
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 claims description 2
- PPJPTAQKIFHZQU-UHFFFAOYSA-N bis(tert-butylimino)tungsten;dimethylazanide Chemical compound C[N-]C.C[N-]C.CC(C)(C)N=[W]=NC(C)(C)C PPJPTAQKIFHZQU-UHFFFAOYSA-N 0.000 claims description 2
- 150000001721 carbon Chemical group 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- AEVRNKXPLOTCBW-UHFFFAOYSA-N carbon monoxide;cobalt;cyclopenta-1,3-diene Chemical compound [Co].[O+]#[C-].[O+]#[C-].C=1C=C[CH-]C=1 AEVRNKXPLOTCBW-UHFFFAOYSA-N 0.000 claims description 2
- NQZFAUXPNWSLBI-UHFFFAOYSA-N carbon monoxide;ruthenium Chemical compound [Ru].[Ru].[Ru].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] NQZFAUXPNWSLBI-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- BKFAZDGHFACXKY-UHFFFAOYSA-N cobalt(II) bis(acetylacetonate) Chemical compound [Co+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O BKFAZDGHFACXKY-UHFFFAOYSA-N 0.000 claims description 2
- ZKXWKVVCCTZOLD-FDGPNNRMSA-N copper;(z)-4-hydroxypent-3-en-2-one Chemical compound [Cu].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O ZKXWKVVCCTZOLD-FDGPNNRMSA-N 0.000 claims description 2
- 150000001925 cycloalkenes Chemical class 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- MGNZXYYWBUKAII-UHFFFAOYSA-N cyclohexa-1,3-diene Chemical compound C1CC=CC=C1 MGNZXYYWBUKAII-UHFFFAOYSA-N 0.000 claims description 2
- VSLPMIMVDUOYFW-UHFFFAOYSA-N dimethylazanide;tantalum(5+) Chemical compound [Ta+5].C[N-]C.C[N-]C.C[N-]C.C[N-]C.C[N-]C VSLPMIMVDUOYFW-UHFFFAOYSA-N 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 claims description 2
- 150000002829 nitrogen Chemical group 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 229910052762 osmium Inorganic materials 0.000 claims description 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 239000004065 semiconductor Substances 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 12
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims 1
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 claims 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 abstract description 7
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 abstract description 7
- -1 ether alkoxide Chemical class 0.000 abstract description 5
- 239000006193 liquid solution Substances 0.000 abstract description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 2
- 150000002527 isonitriles Chemical class 0.000 abstract description 2
- 150000002825 nitriles Chemical class 0.000 abstract description 2
- 150000003950 cyclic amides Chemical class 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 61
- 238000002411 thermogravimetry Methods 0.000 description 20
- 238000002360 preparation method Methods 0.000 description 15
- 239000007788 liquid Substances 0.000 description 11
- SRLSISLWUNZOOB-UHFFFAOYSA-N ethyl(methyl)azanide;zirconium(4+) Chemical compound [Zr+4].CC[N-]C.CC[N-]C.CC[N-]C.CC[N-]C SRLSISLWUNZOOB-UHFFFAOYSA-N 0.000 description 9
- 239000010408 film Substances 0.000 description 9
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 9
- 0 [1*]C1OCOC([3*])C1[2*] Chemical compound [1*]C1OCOC([3*])C1[2*] 0.000 description 8
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 8
- 238000002347 injection Methods 0.000 description 7
- 239000007924 injection Substances 0.000 description 7
- 238000009834 vaporization Methods 0.000 description 7
- 230000008016 vaporization Effects 0.000 description 7
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000008020 evaporation Effects 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000007983 Tris buffer Substances 0.000 description 4
- SAAKEQOBORNMJM-UHFFFAOYSA-N barium;1,2,3,4-tetramethyl-5-propylcyclopentane Chemical compound [Ba].CCC[C]1[C](C)[C](C)[C](C)[C]1C.CCC[C]1[C](C)[C](C)[C](C)[C]1C SAAKEQOBORNMJM-UHFFFAOYSA-N 0.000 description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 4
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 235000019253 formic acid Nutrition 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 235000012431 wafers Nutrition 0.000 description 3
- OXJUCLBTTSNHOF-UHFFFAOYSA-N 5-ethylcyclopenta-1,3-diene;ruthenium(2+) Chemical compound [Ru+2].CC[C-]1C=CC=C1.CC[C-]1C=CC=C1 OXJUCLBTTSNHOF-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- FQNHWXHRAUXLFU-UHFFFAOYSA-N carbon monoxide;tungsten Chemical group [W].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] FQNHWXHRAUXLFU-UHFFFAOYSA-N 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- PGPDZDIKLWZUIR-UHFFFAOYSA-N lanthanum;propylcyclopentane Chemical compound [La].CCC[C]1[CH][CH][CH][CH]1.CCC[C]1[CH][CH][CH][CH]1.CCC[C]1[CH][CH][CH][CH]1 PGPDZDIKLWZUIR-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000012032 thrombin generation assay Methods 0.000 description 2
- 208000014903 transposition of the great arteries Diseases 0.000 description 2
- 239000012691 Cu precursor Substances 0.000 description 1
- BZORFPDSXLZWJF-UHFFFAOYSA-N N,N-dimethyl-1,4-phenylenediamine Chemical compound CN(C)C1=CC=C(N)C=C1 BZORFPDSXLZWJF-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000004699 copper complex Chemical class 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910001338 liquidmetal Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical group O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Images
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
- C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
- C23C16/18—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metallo-organic compounds
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
- C23C16/16—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metal carbonyl compounds
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02612—Formation types
- H01L21/02617—Deposition types
- H01L21/0262—Reduction or decomposition of gaseous compounds, e.g. CVD
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/67005—Apparatus not specifically provided for elsewhere
- H01L21/67011—Apparatus for manufacture or treatment
- H01L21/67155—Apparatus for manufacturing or treating in a plurality of work-stations
- H01L21/67207—Apparatus for manufacturing or treating in a plurality of work-stations comprising a chamber adapted to a particular process
Definitions
- metal source containing precursors for chemical vapor deposition processes including atomic layer deposition for fabricating conformal metal-containing films on substrates such as silicon, silicon oxide, metal nitride, metal oxide and other metal-containing layers using these metal source containing precursors.
- a particularly advantageous way of delivering multiple source containing precursors is to employ neat liquid source containing liquid metal precursors or solutions of metal source precursors dissolved in a solvent, flash to vaporize the mixture, and then deliver the resulting vapors to the reactor.
- the reactions convert the metal source containing precursor to an insoluble or non-volatile product, or to a material of different chemical or physical properties, the elements contained in that product may not reach the substrate and the stoichiometry of the deposited film may not be correct.
- the present invention generally relates to an improvement in metal source containing precursor solutions suitable for use in chemical vapor deposition processes, including cyclic chemical vapor deposition as well as atomic layer deposition, for fabricating conformal metal-containing films on substrates and to such processes.
- the metal source precursor solutions are comprised of (i) at least one metal coordination complex including a metal, to which is coordinatively bound to at least one ligand in a stable complex and (ii) a solvent comprised of an organic amide for such metal source containing precursors.
- the ligand for metal complex is selected from the group consisting of: ⁇ -diketonates, ⁇ -ketoiminates, ⁇ -ketoesters, alkyl, carbonyl, alkylcyclopentadineyl, and alkoxy.
- FIG. 1 is a Thermo Gravimetric Analysis (TGA) of 1.0 M solution of titanium isopropoxide in N-methyl-2-pyrrolidinone.
- FIG. 2 is a TGA of 0.1M solution of tris(2,2,6,6-tetramethyl-3,5-heptanedionate)lanthanum in N-methyl-2-pyrrolidinone.
- FIG. 3 shows TGAs of solutions of tetrakis(ethylmethylamino)zirconium (TEMAZ) in N-methyl-2-pyrrolidinone: A (10% NMP in TEMAZ); B (40% NMP in TEMAZ); C (50% NMP in TEAM).
- A 10% NMP in TEMAZ
- B 40% NMP in TEMAZ
- C 50% NMP in TEAM.
- FIG. 4 is a TGA of 0.3M of tetrakis(dimethylamine)hafnium in N-methyl-2-pyrrolidinone.
- FIG. 5 shows TGAs of solutions of Cu-KI3 in N-methyl-2-pyrrolidinone: 1 (8% NMP in KI3); 2 (12% NMP in KI-3); 3 (27% NMP in KI3).
- the broadly based metal source precursor solutions are comprised of (i) at least one metal coordination complex including a metal, to which is coordinatively bound to at least one ligand in a stable complex.
- Representative metal complexes include ⁇ -diketonates, ⁇ -ketoiminates, ⁇ -diiminates, alkyl metal, metal carbonyl, alkyl metal carbonyl, aryl metal, aryl metal carbonyl, cyclopentadienyl metal, alkylcyclopentadienyl metal, cyclopentadienyl metal isonitrile, cyclopentadienyl metal nitrile, carbonyl cyclopentadienyl metal, metal alkoxide, metal ether alkoxide, and metal amides.
- the ligand can be monodentate, bidentate and multidentate coordinating to the metal atom and the metal is selected from group 2 to 14 elements. Generally the valence of the metal is from 2 to 14
- M is selected from Group 2 to 14, e.g., those having a valence from 2 to 5 and specific examples of metals include Mg, Ca, Sr, Ba, Y, La, Ce, Sm, Tb, Er, Yb, Lu, Ti, Zr, Hf, Fe, Co, Ni, Ru, Ir, Rh, Cu, Al, Sn, and Pb; wherein R 1-3 are linear, branched, or cyclic independently selected from the groups consisting of hydrogen, C 1-10 alkyl, C 1-10 alkenyl, C 3-10 alkylsilyl, C 1-10 alkynyl, C 5 -C 10 cycloaliphatic, C 6-12 aryl, and fluorinated C 1-10 alkyl; wherein x is the integer 2, 3, or 4 based upon the valence of the metal.
- Illustrative ⁇ -diketonate ligands employed in metal source complexes of the present invention include: acetylacetonate or more specifically 2,4-pentanedionate (acac), hexafluoroacetylacetonate or more specifically 1,1,1,5,5,5-hexafluoro-2,4-pentanedionate (hfacac); trifluoroacetylacetonate or more specifically 1,1,1-trifluoro-2,4-pentanedionate (tfacac); tetramethylheptanedionate or more specifically 2,2,6,6-tetramethyl-3,5-heptanedionate (thd); fluorodimethyloctanedionate or more specifically 1,1,1,2,2,3,3-heptafluoro-7,7-dimethyl-4,6-octanedionate (fod); and heptafluoro-dimethyloctaned
- Exemplary metal complexes include Sr(thd) 2 , Ba(thd) 2 , Co(acac) 2 , Ni(acac) 2 , Cu(acac) 2 , Ru(thd) 3 , La(thd) 3 , Y(thd) 3 , Ti(thd) 4 , Hf(thd) 4 , and Zr(thd) 4 .
- M is selected from Group 2 to 14, and specific examples of metals include Mg, Ca, Sr, Ba, Y, La, Ce, Sm, Tb, Er, Yb, Lu, Ti, Zr, Hf, Fe, Co, Ni, Ru, Ir, Rh, Cu, Al, Sn, and Pb; wherein R 1-3 are linear, branched or cyclic independently selected from the groups consisting of hydrogen, C 1-10 alkyl, C 1-10 alkenyl, C 1-10 alkynyl, C 3-10 alkylsilyl, C 5 -C 10 cycloaliphatic, C 6-12 aryl, and fluorinated C 1-10 alkyl; wherein x is the integer 2, 3, or 4 consistent with the valence of M; R 4 is linear, branched or cyclic selected from the group consisting of hydrogen, C 1-10 alkyl, C 1-10 alkenyl, C 1-10 alkynyl, C 3-10 alkylsilyl, C 5 -C 10 cyclo
- M is selected from Group 2 to 13, and specific examples of metals include Mg, Ca, Sr, Ba, Y, La, Ce, Sm, Tb, Er, Yb, Lu, Ti, Zr, Hf, Fe, Co, Ni, Ru, Ir, Rh, Cu, Al, Sn, and Pb; wherein R 1-3 are linear, branched or cyclic independently selected from the groups consisting of hydrogen, C 1-10 alkyl, C 1-10 alkenyl, C 1-10 alkynyl, C 3-10 alkylsilyl, C 5 -C 10 cycloaliphatic, C 6-12 aryl, and fluorinated C 1-10 alkyl; wherein x is the integer 2, 3, or 4.
- R 4-5 also can contain unsaturation bonds and are linear, branched or cyclic independently selected from the groups consisting of hydrogen, C 1-10 alkyl, C 1-10 alkenyl, C 1-10 alkynyl, C 5 -C 10 cycloaliphatic, C 6-12 aryl, and fluorinated C 1-10 alkyl.
- M is a metal ion selected from Group 4 and 5 metals including titanium, zirconium, hafnium, vanadium, niobium, and tantalum; wherein R 1-3 are linear, branched or cyclic independently selected from the groups consisting of C 1-10 alkyl, C 1-10 alkenyl, C 1-10 alkynyl, C 3-10 alkylsilyl, C 5 -C 10 cycloaliphatic, C 6-12 aryl, and fluorinated C 1-10 alkyl R 4 is linear, branched or cyclic selected from the group consisting of C 1-10 alkyl, C 1-10 alkenyl, C 1-10 alkynyl, C 3-10 alkylsilyl, C 5 -C 10 cycloaliphatic, C 6-12 aryl, and fluorinated C 1-10 alkyl; wherein m and n are at least 1 and the sum of m plus n is equal to the valence of the metal M.
- M is a metal ion selected from Group 8, 9, and 10 metals including iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum; wherein R 1-3 are liner, branched or cyclic selected from the groups consisting of C 1-10 alkyl, C 1-10 alkenyl, C 1-10 alkynyl, C 3-10 alkylsilyl, C 5 -C 10 cycloaliphatic, C 6-12 aryl, and fluorinated C 1-10 alkyl; wherein R 4 is linear, branched or cyclic selected from the groups consisting of C 1-10 alkyl, C 1-10 alkenyl, C 1-10 alkynyl, C 5 -C 10 cycloaliphatic, C 6-10 cycloalkene, C 6-12 cycloalkyne, C 6-12 aryl, and fluorinated C 1-10 alkyl; wherein m and n are at least 1 and
- M is a metal ion selected from Group 4 and 5 metals including titanium, zirconium, hafnium, vanadium, niobium, and tantalum; wherein R 1-5 are linear, branched or cyclic independently selected from the group consisting of hydrogen, C 1-10 alkyl, C 1-10 alkenyl, C 1-10 alkynyl, C 3-10 alkylsilyl, C 5 -C 10 cycloaliphatic, C 6-12 aryl, and fluorinated C 1-10 alkyl; wherein m and n are at least 1 and the sum of m plus n is equal to the valence of the metal M.
- M is a metal ion selected from Group 11 metals including copper, silver, and gold;
- R 1-2 are linear, branched or cyclic independently selected from the groups consisting of hydrogen, C 1-10 alkyl, C 1-10 alkenyl, C 1-10 alkynyl, C 3-10 alkylsilyl, C 5 -C 10 cycloaliphatic, C 6-12 aryl, and fluorinated C 1-10 alkyl or halogen;
- R 3-4 are linear or branched independently selected from the groups consisting of C 1-6 alkyl, C 1-6 alkenyl, C 1-6 alkynyl and fluorinated C 1-6 alkyl, preferably R 4 is a 2 to 4 carbon atom linkage;
- R 5-6 are linear, branched or cyclic independently selected from the groups consisting of C 1-10 alkyl, C 1-10 alkenyl, C 1-10 alkynyl, C 5 -C 10 cycloaliphatic, C 6-12 aryl,
- Exemplary metal complexes include Cu(CF 3 C(O)CHC(NCH 2 CH 2 OSiMe 2 C 2 H 3 )CF 3 ), Cu(CF 3 C(O)CHC(NCH 2 CH 2 OSiMe 2 C 2 H 3 )Me), Cu(MeC(O)CHC(NCH 2 CH(Me)OSiMe 2 C 2 H 3 )Me), Cu(MeC(O)CHC(NCH 2 CH 2 OSiMe 2 C 2 H 3 )Me), Cu(MeC(O)CHC(NCH 2 CH 2 N(Me)SiMe 2 C 2 H 3 )Me), Cu(MeC(O)CHC(NCH(Et)CH 2 OSiMe 2 C 2 H 3 )Me).
- Exemplary metal complexes include CoCp 2 , SrCp 2 , Sr( i PrCp) 2 , Sr( i Pr 3 Cp) 2 , BaCp 2 , Ba( i PrCp) 2 , Ba( i Pr 3 Cp) 2 , RuCp 2 , Ru(EtCp) 2 , Ru(MeCp)(EtCp), Ru(DMPD)(EtCp), NiCp 2 , Cp 2 HfMe 2 , and Cp 2 ZrMe 2 .
- metals include Mg, Ca, Sr, Ba, Y, La, Ce, Sm, Tb, Er, Yb, Lu, Fe, Co, Ni, Ru, Ir, Rh
- Exemplary metal complexes include Cp 2 Ru(CO) 2 , (1,3-cyclohexdiene)Ru(CO) 3 , CpRe(CO) 3 , CpCo(CO) 2 and i PrCpRe(CO) 3 .
- M is selected from Group 8 to 10 where specific examples of metals include Fe, Co, Ni, Ru, Ir, and Rh; wherein x is an integer 1, 2, or 3; y is an integer 4 to 12.
- metal complexes include Ru 3 (CO) 12 , W(CO) 6 , Mo(CO) 6 , CO 2 (CO) 8 , and Ni(CO) 4 .
- M is selected from Group 2 to 14 where specific examples of metals include Mg, Ca, Sr, Ba, Y, La, Ce, Sm, Tb, Er, Yb, Lu, Fe, Co, Ni, Ru, Ir, Rh, Cu, Al, and Pb; wherein R is linear, branched or cyclic selected from the groups consisting of C 1-10 alkyl, C 1-10 alkenyl, C 1-10 alkynyl, C 5 -C 10 cycloaliphatic, C 6-12 aryl, and fluorinated C 1-10 alkyl; wherein n is an integer 2, 3, 4 or 5, comprising the valence of M.
- Exemplary metal complexes include Ti( i PrO) 4 , Hf(OBu t ) 4 , Zr(OBu t ) 4 , and Ta 2 (OEt) 10 .
- M is selected from Group 2 to 14 where specific examples of metals include Mg, Ca, Sr, Ba, Y, La, Ce, Sm, Tb, Er, Yb, Lu, Fe, Co, Ni, Ru, Ir, Rh, Cu, Al, and Pb; wherein R 1-2 are liner, branched or cyclic independently selected from the groups consisting of C 1-10 alkyl, C 1-10 alkenyl, C 1-10 alkynyl, C 3-10 alkylsilyl, C 5 -C 10 cycloaliphatic, C 6-12 aryl, and fluorinated C 1-10 alkyl; wherein n is the integer 2, 3, 4, or 5, comprising the valence of M.
- Exemplary metal complexes include tetrakis(dimethylamino)titanium (TDMAT), tetrakis(diethylamino)titanium (TDEAT), tetrakis(ethylmethyl)titanium (TEMAT), tetrakis(dimethylamino)zirconium (TDMAZ), tetrakis(diethylamino)zirconium (TDEAZ), tetrakis(ethylmethyl)zirconium (TEMAZ), tetrakis(dimethylamino)hafnium (TDMAH), tetrakis(diethylamino)hafnium (TDEAH), tetrakis(ethylmethyl)hafnium (TEMAH), tert-butylimino tri(diethylamino)tantalum (TBTDET), tert-butylimino tri(dimethylamino)tantalum (
- the ligand groups of the metal source containing precursor complexes in the broad practice of the present invention may be variously substituted to produce a wide variety of materials to optimize volatility, stability and film purity.
- the metal source precursor comprises two or more metal source containing precursor complexes
- the ligands of the various metal source containing precursor complexes should be either: (a) identical, to result in degenerative ligand exchange (wherein any ligand exchange involves replacement of the ligand group by the same type ligand from another constituent of the multicomponent solution); or, (b) resistant to any detrimental non-degenerative ligand exchange in relation to one another, which would substantially impair or preclude the efficacy of the metal source complex for its intended purpose.
- the metal source containing precursors generally are selected for solution applications on the basis of the following criteria: (i) the metal centers in the coordinated complexes should be as coordinatively saturated as possible, and in such respect multidentate ligands are preferred which occupy multiple coordination sites in the source precursor complex; (ii) the ligands preferably comprise sterically bulky groups such as isopropyl, t-butyl, and neopentyl, which prevent intermolecular interaction of the metal centers and thus hinder ligand exchange reaction and (iii) each of the individual metal source precursors in the solution should have a suitable vapor pressure characteristic, e.g., a vapor pressure of at least 0.001 Torr at the temperature and pressure conditions involved in their volatilization.
- a suitable vapor pressure characteristic e.g., a vapor pressure of at least 0.001 Torr at the temperature and pressure conditions involved in their volatilization.
- the solvent medium employed in formulating the metal source precursor solutions in accordance with the present invention is the organic amide class of the form, RCONR′R′′, wherein R and R′ are linear or branched alkyl having from 1-10 carbon atoms or R and R′ can be connected to form a cyclic group (CH 2 ) n , wherein n is from 4-6, preferably 5, and R′′ is alkyl having from 1 to 4 carbon atoms and cycloalkyl.
- N-methyl, N-ethyl and N-cyclohexyl 2-pyrrolidinones are examples of the preferred solvents of the organic amide class.
- the metal source precursor solutions of the present invention may be readily employed in chemical vapor deposition (CVD) applications including atomic layer deposition (ALD) for forming a metal-containing film on a substrate by the steps of volatilizing the metal source precursor liquid solution to yield a metal source vapor, and contacting the metal source vapor with the substrate, to deposit the metal-containing film thereon.
- CVD chemical vapor deposition
- ALD atomic layer deposition
- FIG. 1 is a TGA of the 1.M solution of titanium isopropoxide in N-methyl-2-pyrrolidinone, suggesting a smooth vaporization process in the temperature range of 20 to 400° C. This vaporization behavior suggests the solution can be employed either via bubbling or direct liquid injection for chemical vapor deposition or atomic vapor deposition.
- FIG. 2 is a TGA of 0.1M solution of tris(2,2,6,6-tetramethyl-3,5-heptanedionate)lanthanum in N-methyl-2-pyrrolidinone, indicating there are two vaporization processes, the first is mainly for NMP and the second tris(2,2,6,6-tetramethyl-3,5-heptanedionate)lanthanum.
- This vaporization behavior suggests the solution can be only employed via direct liquid injection for chemical vapor deposition or atomic vapor deposition.
- TEMAZ tetrakis(ethylmethylamino)zirconium
- FIG. 3 shows TGA diagrams of the solutions, suggesting that direct liquid injection with a lower concentration is preferred.
- FIG. 4 is a TGA graph of a 0.3M yellow solution of tetrakis(dimethylamino)hafnium (TDMAH) in N-methyl-2-pyrrolidinone, suggesting that direct liquid injection with lower concentration is preferred.
- TDMAH tetrakis(dimethylamino)hafnium
- TDEAZ tetrakis(diethylamino)zirconium
- Table 2 shows the weights of the copper metal complex Cu-KI3 (i.e., (CF 3 C(O)CHC(NCH 2 CH 2 OSiMe 2 C 2 H 3 )CF 3 )Cu) mixed with dry deoxygenated NMP solvent under nitrogen. After thoroughly mixing, three solutions 1, 2 and 3 were individually tested in a TGA/DSC (Differential Scanning Calorimetry) apparatus.
- Cu-KI3 i.e., (CF 3 C(O)CHC(NCH 2 CH 2 OSiMe 2 C 2 H 3 )CF 3
- a Gartek single wafer CVD reactor fitted with a Direct Liquid Injector (DLI) system was used to individually process ruthenium and titanium coated silicon wafers at a process chamber pressure of 1 Torr and wafer temperature of 150° C.
- the copper precursor was utilized as a 3:1 by weight ratio of KI3 dissolved in dry N-methylpyrolidone (NMP) and injected into the vaporizer at a rate of 41 mg/min using an evaporation temperature of 100° C. with an argon carrier gas flow of 250 sccm.
- Formic acid vapor was delivered by the DLI of 82 mg of liquid formic acid/min using an evaporation temperature of 65° C. with an argon carrier gas flow rate of 100 sccm. Run time was 30 minutes.
- Titanium nitride 386.7 nm of copper (as confirmed by EDX analysis) were deposited to give, after correcting for the titanium nitride underlayer, a resistivity of 2.3 ⁇ cm.
Abstract
Description
- This patent application claims the benefit of U.S. Provisional Patent Application Ser. No. 60/911,970 filed 16 Apr. 2007.
- The semiconductor fabrication industry continues to use metal source containing precursors for chemical vapor deposition processes including atomic layer deposition for fabricating conformal metal-containing films on substrates such as silicon, silicon oxide, metal nitride, metal oxide and other metal-containing layers using these metal source containing precursors. In the fabrication process, a particularly advantageous way of delivering multiple source containing precursors is to employ neat liquid source containing liquid metal precursors or solutions of metal source precursors dissolved in a solvent, flash to vaporize the mixture, and then deliver the resulting vapors to the reactor. If in the fabrication process the reactions convert the metal source containing precursor to an insoluble or non-volatile product, or to a material of different chemical or physical properties, the elements contained in that product may not reach the substrate and the stoichiometry of the deposited film may not be correct.
- In certain instances, such problems can be avoided sometimes by using identical ligands coordinated to the metals to make ligand exchange a degenerate reaction (i.e., where the exchanging ligand is identical to the original ligand). The foregoing problems also may be encountered where the precursor is provided in a liquid solution and the solvent contains moieties which react with the metal or ligands of the precursor to produce undesirable reaction by-products.
- The following references are illustrative of metal source containing precursor solutions for use in preparing conformal metal-containing films: U.S. Pat. No. 5,820,664; U.S. Pat. No. 6,225,237; U.S. Pat. No. 6,984,591; US2006/0269667; Lee, D.-J., S.-W. Kang and S.-W. Rhee (2001). “Chemical vapor deposition of ruthenium oxide thin films from Ru(tmhd)3 using direct liquid injection.” Thin Solid Films 413: 237; U.S. Pat. No. 6,111,122; Moshnyaga, V., I. Khoroshun, A. Sidorenko, P. Petrenko, A. Weidinger, M. Zeitler, B. Rauschenbach, R. Tidecks and K. Samwer (1999). “Preparation of rare-earth manganite-oxide thin films by metalorganic aerosol deposition technique.” Applied Physics Letters 74(19): 2842-2844; U.S. Pat. No. 5,900,279; U.S. Pat. No. 5,916,359; and JP 06234779.
- The present invention generally relates to an improvement in metal source containing precursor solutions suitable for use in chemical vapor deposition processes, including cyclic chemical vapor deposition as well as atomic layer deposition, for fabricating conformal metal-containing films on substrates and to such processes. More specifically, the metal source precursor solutions are comprised of (i) at least one metal coordination complex including a metal, to which is coordinatively bound to at least one ligand in a stable complex and (ii) a solvent comprised of an organic amide for such metal source containing precursors. Preferably the ligand for metal complex is selected from the group consisting of: β-diketonates, β-ketoiminates, β-ketoesters, alkyl, carbonyl, alkylcyclopentadineyl, and alkoxy.
- Some of the advantages which may be available through the use of these solutions include the following:
- an ability to provide metal source precursor compositions in liquid solution form to simultaneously deliver the constituent metal(s) to a deposition locus such as a chemical vapor deposition or atomic layer deposition chamber;
- an ability to provide solutions which are resistant to deleterious ligand exchange reactions;
- an ability to provide a solution containing a high boiling linear or cyclic organic amide;
- an ability to stabilize a metal complex in both liquid and gas phase via coordinating the organic amide to the metal center, an ability to promote the vaporization of the metal complex via a direct liquid injection device; and,
- an ability to tune the physical properties of the precursor solution such as viscosity for easy delivery.
-
FIG. 1 is a Thermo Gravimetric Analysis (TGA) of 1.0 M solution of titanium isopropoxide in N-methyl-2-pyrrolidinone. -
FIG. 2 is a TGA of 0.1M solution of tris(2,2,6,6-tetramethyl-3,5-heptanedionate)lanthanum in N-methyl-2-pyrrolidinone. -
FIG. 3 shows TGAs of solutions of tetrakis(ethylmethylamino)zirconium (TEMAZ) in N-methyl-2-pyrrolidinone: A (10% NMP in TEMAZ); B (40% NMP in TEMAZ); C (50% NMP in TEAM). -
FIG. 4 is a TGA of 0.3M of tetrakis(dimethylamine)hafnium in N-methyl-2-pyrrolidinone. -
FIG. 5 shows TGAs of solutions of Cu-KI3 in N-methyl-2-pyrrolidinone: 1 (8% NMP in KI3); 2 (12% NMP in KI-3); 3 (27% NMP in KI3). - In reference to the above, the broadly based metal source precursor solutions are comprised of (i) at least one metal coordination complex including a metal, to which is coordinatively bound to at least one ligand in a stable complex. Representative metal complexes include β-diketonates, β-ketoiminates, β-diiminates, alkyl metal, metal carbonyl, alkyl metal carbonyl, aryl metal, aryl metal carbonyl, cyclopentadienyl metal, alkylcyclopentadienyl metal, cyclopentadienyl metal isonitrile, cyclopentadienyl metal nitrile, carbonyl cyclopentadienyl metal, metal alkoxide, metal ether alkoxide, and metal amides. The ligand can be monodentate, bidentate and multidentate coordinating to the metal atom and the metal is selected from
group 2 to 14 elements. Generally the valence of the metal is from 2 to 5. - Variations of the above metal source containing precursors are represented by the generalized formulas:
- (a) Metal β-diketonates having the formula:
- wherein M is selected from
Group 2 to 14, e.g., those having a valence from 2 to 5 and specific examples of metals include Mg, Ca, Sr, Ba, Y, La, Ce, Sm, Tb, Er, Yb, Lu, Ti, Zr, Hf, Fe, Co, Ni, Ru, Ir, Rh, Cu, Al, Sn, and Pb; wherein R1-3 are linear, branched, or cyclic independently selected from the groups consisting of hydrogen, C1-10 alkyl, C1-10 alkenyl, C3-10 alkylsilyl, C1-10 alkynyl, C5-C10 cycloaliphatic, C6-12 aryl, and fluorinated C1-10 alkyl; wherein x is theinteger 2, 3, or 4 based upon the valence of the metal. - Illustrative β-diketonate ligands employed in metal source complexes of the present invention include: acetylacetonate or more specifically 2,4-pentanedionate (acac), hexafluoroacetylacetonate or more specifically 1,1,1,5,5,5-hexafluoro-2,4-pentanedionate (hfacac); trifluoroacetylacetonate or more specifically 1,1,1-trifluoro-2,4-pentanedionate (tfacac); tetramethylheptanedionate or more specifically 2,2,6,6-tetramethyl-3,5-heptanedionate (thd); fluorodimethyloctanedionate or more specifically 1,1,1,2,2,3,3-heptafluoro-7,7-dimethyl-4,6-octanedionate (fod); and heptafluoro-dimethyloctanedionate. Exemplary metal complexes include Sr(thd)2, Ba(thd)2, Co(acac)2, Ni(acac)2, Cu(acac)2, Ru(thd)3, La(thd)3, Y(thd)3, Ti(thd)4, Hf(thd)4, and Zr(thd)4.
- (b) Metal β-ketoiminates having the formula:
- wherein M is selected from
Group 2 to 14, and specific examples of metals include Mg, Ca, Sr, Ba, Y, La, Ce, Sm, Tb, Er, Yb, Lu, Ti, Zr, Hf, Fe, Co, Ni, Ru, Ir, Rh, Cu, Al, Sn, and Pb; wherein R1-3 are linear, branched or cyclic independently selected from the groups consisting of hydrogen, C1-10 alkyl, C1-10 alkenyl, C1-10 alkynyl, C3-10 alkylsilyl, C5-C10 cycloaliphatic, C6-12 aryl, and fluorinated C1-10 alkyl; wherein x is theinteger 2, 3, or 4 consistent with the valence of M; R4 is linear, branched or cyclic selected from the group consisting of hydrogen, C1-10 alkyl, C1-10 alkenyl, C1-10 alkynyl, C3-10 alkylsilyl, C5-C10 cycloaliphatic, C6-12 aryl, and fluorinated C1-10 alkyl. - (c) Metal β-diiminates having the formula:
- wherein M is selected from
Group 2 to 13, and specific examples of metals include Mg, Ca, Sr, Ba, Y, La, Ce, Sm, Tb, Er, Yb, Lu, Ti, Zr, Hf, Fe, Co, Ni, Ru, Ir, Rh, Cu, Al, Sn, and Pb; wherein R1-3 are linear, branched or cyclic independently selected from the groups consisting of hydrogen, C1-10 alkyl, C1-10 alkenyl, C1-10 alkynyl, C3-10 alkylsilyl, C5-C10 cycloaliphatic, C6-12 aryl, and fluorinated C1-10 alkyl; wherein x is theinteger 2, 3, or 4. R4-5 also can contain unsaturation bonds and are linear, branched or cyclic independently selected from the groups consisting of hydrogen, C1-10 alkyl, C1-10 alkenyl, C1-10 alkynyl, C5-C10 cycloaliphatic, C6-12 aryl, and fluorinated C1-10 alkyl. - (d) Metal Alkoxy β-diketonates having the formula:
- wherein M is a metal ion selected from Group 4 and 5 metals including titanium, zirconium, hafnium, vanadium, niobium, and tantalum; wherein R1-3 are linear, branched or cyclic independently selected from the groups consisting of C1-10 alkyl, C1-10 alkenyl, C1-10 alkynyl, C3-10 alkylsilyl, C5-C10 cycloaliphatic, C6-12 aryl, and fluorinated C1-10 alkyl R4 is linear, branched or cyclic selected from the group consisting of C1-10 alkyl, C1-10 alkenyl, C1-10 alkynyl, C3-10 alkylsilyl, C5-C10 cycloaliphatic, C6-12 aryl, and fluorinated C1-10 alkyl; wherein m and n are at least 1 and the sum of m plus n is equal to the valence of the metal M. Exemplary metal complexes include Ti(thd)2(OBut)2, Hf(thd)2(OBut)2, and Zr(thd)2(OBut)2.
- (e) Alkyl Metal β-diketonates having the formula:
- wherein M is a metal ion selected from Group 8, 9, and 10 metals including iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum; wherein R1-3 are liner, branched or cyclic selected from the groups consisting of C1-10 alkyl, C1-10 alkenyl, C1-10 alkynyl, C3-10 alkylsilyl, C5-C10 cycloaliphatic, C6-12 aryl, and fluorinated C1-10 alkyl; wherein R4 is linear, branched or cyclic selected from the groups consisting of C1-10 alkyl, C1-10 alkenyl, C1-10 alkynyl, C5-C10 cycloaliphatic, C6-10 cycloalkene, C6-12 cycloalkyne, C6-12 aryl, and fluorinated C1-10 alkyl; wherein m and n are at least 1 and the sum of m plus n is equal to the valence of the metal M and n is equal to the valence of the metal M if R4 is a neutral ligand. Exemplary metal complexes but not limited bis(2,2,6,6-tetramethyl-3,5-heptanedionato)(1,5-cyclo-octadiene)ruthenium(II).
- (f) Metal Alkoxy β-ketoiminates with the formula:
- wherein M is a metal ion selected from Group 4 and 5 metals including titanium, zirconium, hafnium, vanadium, niobium, and tantalum; wherein R1-5 are linear, branched or cyclic independently selected from the group consisting of hydrogen, C1-10 alkyl, C1-10 alkenyl, C1-10 alkynyl, C3-10 alkylsilyl, C5-C10 cycloaliphatic, C6-12 aryl, and fluorinated C1-10 alkyl; wherein m and n are at least 1 and the sum of m plus n is equal to the valence of the metal M.
- (g) Metal β-ketoiminates with the formula:
- wherein M is a metal ion selected from Group 11 metals including copper, silver, and gold; wherein R1-2 are linear, branched or cyclic independently selected from the groups consisting of hydrogen, C1-10 alkyl, C1-10 alkenyl, C1-10 alkynyl, C3-10 alkylsilyl, C5-C10 cycloaliphatic, C6-12 aryl, and fluorinated C1-10 alkyl or halogen; R3-4 are linear or branched independently selected from the groups consisting of C1-6 alkyl, C1-6 alkenyl, C1-6 alkynyl and fluorinated C1-6 alkyl, preferably R4 is a 2 to 4 carbon atom linkage; R5-6 are linear, branched or cyclic independently selected from the groups consisting of C1-10 alkyl, C1-10 alkenyl, C1-10 alkynyl, C5-C10 cycloaliphatic, C6-12 aryl, fluorinated C1-10 alkyl or connected to form a ring containing carbon, oxygen, or nitrogen atoms; X is either a carbon or a silicon, and Y is either an oxygen, or a nitrogen substituted with a hydrogen, C1-6 alkyl or C6-10 aryl group. Exemplary metal complexes include Cu(CF3C(O)CHC(NCH2CH2OSiMe2C2H3)CF3), Cu(CF3C(O)CHC(NCH2CH2OSiMe2C2H3)Me), Cu(MeC(O)CHC(NCH2CH(Me)OSiMe2C2H3)Me), Cu(MeC(O)CHC(NCH2CH2OSiMe2C2H3)Me), Cu(MeC(O)CHC(NCH2CH2N(Me)SiMe2C2H3)Me), Cu(MeC(O)CHC(NCH(Et)CH2OSiMe2C2H3)Me).
- (h) Metal alkyl having the formula:
-
MR1 xR2 y - wherein M is selected from
Group 2 to 14 where specific examples of metals include Mg, Ca, Sr, Ba, Y, La, Ce, Sm, Tb, Er, Yb, Lu, Fe, Co, Ni, Ru, Ir, Rh, Cu, Al, and Pb; wherein R1 and R2 are linear, branched or cyclic independently selected from the groups consisting of hydrogen, C1-10 alkyl, C1-10 alkenyl, C1-10 alkynyl, C5-C10 cycloaliphatic, C3-10 alkylsilyl, C6-12 aryl, and fluorinated C1-10 alkyl, cyclopendienyl (Cp) and alkylcyclopendienyl; and wherein x is theinteger integer - (i) Alkyl metal carbonyl having the formula:
-
(CO)yMRx - wherein M is selected from
Group 2 to 14 where specific examples of metals include Mg, Ca, Sr, Ba, Y, La, Ce, Sm, Tb, Er, Yb, Lu, Fe, Co, Ni, Ru, Ir, Rh, Cu, Al, and Pb; wherein R is linear, branched or cyclic selected from the groups consisting of C1-10 alkyl, C1-10 alkenyl, C1-10 alkynyl, C5-C10 cycloaliphatic, C3-10 alkylsilyl, C6-12 aryl, and fluorinated C1-10 alkyl, cyclopendienyl (Cp) and alkylcyclopendienyl; wherein x=2, 3, 4; y=1, or, 2, or 3, or 4 and x=the valence of M. Exemplary metal complexes include Cp2Ru(CO)2, (1,3-cyclohexdiene)Ru(CO)3, CpRe(CO)3, CpCo(CO)2 and iPrCpRe(CO)3. - (j) Metal carbonyl with the formula:
-
Mx(CO)y - wherein M is selected from Group 8 to 10 where specific examples of metals include Fe, Co, Ni, Ru, Ir, and Rh; wherein x is an
integer 1, 2, or 3; y is an integer 4 to 12. Exemplary metal complexes include Ru3(CO)12, W(CO)6, Mo(CO)6, CO2(CO)8, and Ni(CO)4. - (k) Metal alkoxide with the formula:
-
M(OR)n - wherein M is selected from
Group 2 to 14 where specific examples of metals include Mg, Ca, Sr, Ba, Y, La, Ce, Sm, Tb, Er, Yb, Lu, Fe, Co, Ni, Ru, Ir, Rh, Cu, Al, and Pb; wherein R is linear, branched or cyclic selected from the groups consisting of C1-10 alkyl, C1-10 alkenyl, C1-10 alkynyl, C5-C10 cycloaliphatic, C6-12 aryl, and fluorinated C1-10 alkyl; wherein n is aninteger 2, 3, 4 or 5, comprising the valence of M. Exemplary metal complexes include Ti(iPrO)4, Hf(OBut)4, Zr(OBut)4, and Ta2(OEt)10. - (i) Metal amides with the formula:
-
M(NR1R2)n - wherein M is selected from
Group 2 to 14 where specific examples of metals include Mg, Ca, Sr, Ba, Y, La, Ce, Sm, Tb, Er, Yb, Lu, Fe, Co, Ni, Ru, Ir, Rh, Cu, Al, and Pb; wherein R1-2 are liner, branched or cyclic independently selected from the groups consisting of C1-10 alkyl, C1-10 alkenyl, C1-10 alkynyl, C3-10 alkylsilyl, C5-C10 cycloaliphatic, C6-12 aryl, and fluorinated C1-10 alkyl; wherein n is theinteger 2, 3, 4, or 5, comprising the valence of M. - Exemplary metal complexes include tetrakis(dimethylamino)titanium (TDMAT), tetrakis(diethylamino)titanium (TDEAT), tetrakis(ethylmethyl)titanium (TEMAT), tetrakis(dimethylamino)zirconium (TDMAZ), tetrakis(diethylamino)zirconium (TDEAZ), tetrakis(ethylmethyl)zirconium (TEMAZ), tetrakis(dimethylamino)hafnium (TDMAH), tetrakis(diethylamino)hafnium (TDEAH), tetrakis(ethylmethyl)hafnium (TEMAH), tert-butylimino tri(diethylamino)tantalum (TBTDET), tert-butylimino tri(dimethylamino)tantalum (TBTDMT), tert-butylimino tri(ethylmethylamino)tantalum (TBTEMT), ethyllimino tri(diethylamino)tantalum (EITDET), ethyllimino tri(dimethylamino)tantalum (EITDMT), ethyllimino tri(ethylmethylamino)tantalum (EITEMT), tert-amylimino tri(dimethylamino)tantalum (TAIMAT), tert-amylimino tri(diethylamino)tantalum, pentakis(dimethylamino)tantalum, tert-amylimino tri(ethylmethylamino)tantalum, bis(tert-butylimino)bis(dimethylamino)tungsten (BTBMW), bis(tert-butylimino)bis(diethylamino)tungsten, bis(tert-butylimino)bis(ethylmethylamino)tungsten.
- Summarizing, the ligand groups of the metal source containing precursor complexes in the broad practice of the present invention may be variously substituted to produce a wide variety of materials to optimize volatility, stability and film purity. Preferably, when the metal source precursor comprises two or more metal source containing precursor complexes, the ligands of the various metal source containing precursor complexes should be either: (a) identical, to result in degenerative ligand exchange (wherein any ligand exchange involves replacement of the ligand group by the same type ligand from another constituent of the multicomponent solution); or, (b) resistant to any detrimental non-degenerative ligand exchange in relation to one another, which would substantially impair or preclude the efficacy of the metal source complex for its intended purpose.
- The metal source containing precursors generally are selected for solution applications on the basis of the following criteria: (i) the metal centers in the coordinated complexes should be as coordinatively saturated as possible, and in such respect multidentate ligands are preferred which occupy multiple coordination sites in the source precursor complex; (ii) the ligands preferably comprise sterically bulky groups such as isopropyl, t-butyl, and neopentyl, which prevent intermolecular interaction of the metal centers and thus hinder ligand exchange reaction and (iii) each of the individual metal source precursors in the solution should have a suitable vapor pressure characteristic, e.g., a vapor pressure of at least 0.001 Torr at the temperature and pressure conditions involved in their volatilization.
- The solvent medium employed in formulating the metal source precursor solutions in accordance with the present invention is the organic amide class of the form, RCONR′R″, wherein R and R′ are linear or branched alkyl having from 1-10 carbon atoms or R and R′ can be connected to form a cyclic group (CH2)n, wherein n is from 4-6, preferably 5, and R″ is alkyl having from 1 to 4 carbon atoms and cycloalkyl. N-methyl, N-ethyl and N-cyclohexyl 2-pyrrolidinones are examples of the preferred solvents of the organic amide class.
- The metal source precursor solutions of the present invention may be readily employed in chemical vapor deposition (CVD) applications including atomic layer deposition (ALD) for forming a metal-containing film on a substrate by the steps of volatilizing the metal source precursor liquid solution to yield a metal source vapor, and contacting the metal source vapor with the substrate, to deposit the metal-containing film thereon.
- The following examples illustrate the preparation of the metal-containing complexes as precursor solutions in metal-containing film deposition processes and their use in a chemical vapor deposition process.
- To a 2 mL vial, a faint yellow orange solution of titanium isopropoxide (0.10 g, 0.35 mmol) and 0.35 mL N-methyl-2-pyrrolidinone (NMP) was prepared. The solution was kept at room temperature over night and did not show any visible change.
FIG. 1 is a TGA of the 1.M solution of titanium isopropoxide in N-methyl-2-pyrrolidinone, suggesting a smooth vaporization process in the temperature range of 20 to 400° C. This vaporization behavior suggests the solution can be employed either via bubbling or direct liquid injection for chemical vapor deposition or atomic vapor deposition. - To a 2 mL vial, a clear solution of La(thd)3) (0.05 g, 0.07 mmol) and 0.78 mL NMP was prepared.
FIG. 2 is a TGA of 0.1M solution of tris(2,2,6,6-tetramethyl-3,5-heptanedionate)lanthanum in N-methyl-2-pyrrolidinone, indicating there are two vaporization processes, the first is mainly for NMP and the second tris(2,2,6,6-tetramethyl-3,5-heptanedionate)lanthanum. This vaporization behavior suggests the solution can be only employed via direct liquid injection for chemical vapor deposition or atomic vapor deposition. - Three solutions of tetrakis(ethylmethylamino)zirconium (TEMAZ) in NMP were prepared according to Table 1. All are clear yellow solutions.
-
TABLE 1 TEMAZ Sample (g) NMP (g) A 0.2 1.8 B 0.24 0.35 C 0.2 0.2 -
FIG. 3 shows TGA diagrams of the solutions, suggesting that direct liquid injection with a lower concentration is preferred. - The procedure of Example 1 is followed in preparing the above solution.
FIG. 4 is a TGA graph of a 0.3M yellow solution of tetrakis(dimethylamino)hafnium (TDMAH) in N-methyl-2-pyrrolidinone, suggesting that direct liquid injection with lower concentration is preferred. - To a 2 mL vial, a clear orange solution of tetrakis(diethylamino)zirconium (TDEAZ) (0.05 g, 0.07 mmol) and 0.27 g of N-cyclohexyl-2-pyrrolidinone was prepared. The TGA graph indicates the solution is volatile and can be used as precursor source in a CVD or ALD process.
- To a 2 mL vial, a clear yellow solution of tungsten carbonyl (0.10 g, 0.17 mmol) and 12 g of N-methyl-2-pyrrolidinone was prepared. The TGA graph indicates the solution is volatile and can be used as precursor source for CVD or ALD.
- To a 2 mL vial, a clear orange solution of bis(2,2,6,6-tetramethyl-3,5-heptanedionato)(1,5-cyclo-octadiene)ruthenium(II) (0.10 g, 0.28 mmol) and 20 g of N-methyl-2-pyrrolidinone was prepared. The TGA graph indicates the solution is volatile and can be used as precursor source for CVD or ALD.
- Table 2 below shows the weights of the copper metal complex Cu-KI3 (i.e., (CF3C(O)CHC(NCH2CH2OSiMe2C2H3)CF3)Cu) mixed with dry deoxygenated NMP solvent under nitrogen. After thoroughly mixing, three
solutions 1, 2 and 3 were individually tested in a TGA/DSC (Differential Scanning Calorimetry) apparatus. - In this system, a small sample of 1, 2 or 3 was placed in a microbalance and a steady flow of nitrogen passed over the sample as it was steadily heated. Evaporation is registered as weight loss, manifest as a smooth curve down to almost complete evaporation. Since all three samples do not show two stages of evaporation per sample, i.e., the solvent evaporates first and then the copper complex evaporates, it is evident that these mixtures represent excellent blends for Direct Liquid Injection (DLI) type delivery for a CVD or ALD process. The TGA graphs are shown in
FIG. 5 . -
TABLE 2 NMP added to Cu—KI3 Sample Weight of Cu—KI3 Weight of NMP Wt % age NMP added 1 0.787 g 0.063 g 8.0 2 0.284 g 0.035 g 12.0 3 0.145 g 0.039 g 27.0 - To a 2 mL vial, an amber solution of bis(ethylcyclopentadienyl)ruthenium (1.00 g, 2.88 mmol) and 2.97 g of N-methyl-2-pyrrolidinone was prepared. The TGA graph indicates the solution is completely vaporized, leaving no residue.
- To a 2 mL vial, a clear yellow solution of bis(n-propyltetramethyl cyclopentadienyl)barium (0.14 g, 0.30 mmol) and 1.24 g of N-methyl-2-pyrrolidinone was prepared. The TGA graph shows the solution is more volatile than pure bis(n-propyltetramethylcyclopentadienyl)barium, suggesting NMP enhances the vaporization of bis(n-propyltetramethylcyclopentadienyl)barium.
- To a 2 mL vial, a clear solution of tris(i-propylcyclopentadienyl)lanthanum (0.21 g, 0.46 mmol) and 0.94 g of N-methyl-2-pyrrolidinone was prepared. The TGA graph indicates the solution is volatile and can be used as precursor source for CVD or ALD.
- To a 2 mL vial, a yellow solution of bis(2,2,6,6-tetramethyl-3,5-heptanedionate)strontium (0.23 g, 0.51 mmol) and 1.38 g of N-methyl-2-pyrrolidinone was prepared. The TGA graph shows the solution is more volatile than pure bis(2,2,6,6-tetramethyl-3,5-heptanedionate)strontium, suggesting NMP enhances the vaporization of bis(2,2,6,6-tetramethyl-3,5-heptanedionate)strontium.
- To a 2 mL vial, a foggy white solution of bis(2,2,6,6-tetramethyl-3,5-heptanedionate)barium (0.14 g, 0.28 mmol) and 1.14 g of N-methyl-2-pyrrolidinone was prepared. The TGA graph indicates the solution is volatile and can be used as precursor source for CVD or ALD.
- Process details: A Gartek single wafer CVD reactor fitted with a Direct Liquid Injector (DLI) system was used to individually process ruthenium and titanium coated silicon wafers at a process chamber pressure of 1 Torr and wafer temperature of 150° C. The copper precursor was utilized as a 3:1 by weight ratio of KI3 dissolved in dry N-methylpyrolidone (NMP) and injected into the vaporizer at a rate of 41 mg/min using an evaporation temperature of 100° C. with an argon carrier gas flow of 250 sccm. Formic acid vapor was delivered by the DLI of 82 mg of liquid formic acid/min using an evaporation temperature of 65° C. with an argon carrier gas flow rate of 100 sccm. Run time was 30 minutes.
- Results: Ruthenium: 427.5 nm of copper (as confirmed by EDX (energy dispersive x-ray) analysis) were deposited to give, after correcting for the ruthenium underlayer conductivity, a resistivity of 2.6 μΩcm.
- Results: Titanium nitride: 386.7 nm of copper (as confirmed by EDX analysis) were deposited to give, after correcting for the titanium nitride underlayer, a resistivity of 2.3 μΩcm.
Claims (17)
MR1 xR2 y
(CO)yMRx
Mx(CO)y
M(OR)n
and
M(NR1R2)n
RCONR′R″
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TW200902759A (en) | 2009-01-16 |
EP1983073A1 (en) | 2008-10-22 |
KR20080093393A (en) | 2008-10-21 |
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