JP4347855B2 - 循環堆積による金属ケイ素窒化物膜の調製 - Google Patents
循環堆積による金属ケイ素窒化物膜の調製 Download PDFInfo
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- JP4347855B2 JP4347855B2 JP2006036223A JP2006036223A JP4347855B2 JP 4347855 B2 JP4347855 B2 JP 4347855B2 JP 2006036223 A JP2006036223 A JP 2006036223A JP 2006036223 A JP2006036223 A JP 2006036223A JP 4347855 B2 JP4347855 B2 JP 4347855B2
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- Prior art keywords
- bis
- tert
- tetrakis
- tantalum
- deposition method
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 71
- 239000002184 metal Substances 0.000 title claims abstract description 69
- 230000008021 deposition Effects 0.000 title claims abstract description 63
- 125000004122 cyclic group Chemical group 0.000 title claims abstract description 61
- 229910052581 Si3N4 Inorganic materials 0.000 title claims abstract description 51
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 71
- 239000002243 precursor Substances 0.000 claims abstract description 51
- 150000001408 amides Chemical class 0.000 claims abstract description 42
- 239000000758 substrate Substances 0.000 claims abstract description 25
- -1 cyclic alkyl Chemical group 0.000 claims abstract description 12
- DVHMVRMYGHTALQ-UHFFFAOYSA-N silylhydrazine Chemical class NN[SiH3] DVHMVRMYGHTALQ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims abstract description 4
- 125000003709 fluoroalkyl group Chemical group 0.000 claims abstract description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 4
- 125000005353 silylalkyl group Chemical group 0.000 claims abstract description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 4
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 4
- 238000000151 deposition Methods 0.000 claims description 91
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 47
- VYIRVGYSUZPNLF-UHFFFAOYSA-N n-(tert-butylamino)silyl-2-methylpropan-2-amine Chemical group CC(C)(C)N[SiH2]NC(C)(C)C VYIRVGYSUZPNLF-UHFFFAOYSA-N 0.000 claims description 47
- 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 45
- 238000000231 atomic layer deposition Methods 0.000 claims description 32
- 238000005229 chemical vapour deposition Methods 0.000 claims description 27
- 229910021529 ammonia Inorganic materials 0.000 claims description 23
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 21
- 238000010926 purge Methods 0.000 claims description 20
- 229910000077 silane Inorganic materials 0.000 claims description 20
- 239000007789 gas Substances 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 17
- 239000012634 fragment Substances 0.000 claims description 16
- 239000006227 byproduct Substances 0.000 claims description 13
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 11
- 150000003377 silicon compounds Chemical class 0.000 claims description 10
- 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 9
- 238000005137 deposition process Methods 0.000 claims description 8
- LNKYFCABELSPAN-UHFFFAOYSA-N ethyl(methyl)azanide;titanium(4+) Chemical compound [Ti+4].CC[N-]C.CC[N-]C.CC[N-]C.CC[N-]C LNKYFCABELSPAN-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 8
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical group [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 claims description 6
- 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 6
- 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 6
- 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 6
- 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 6
- NPEOKFBCHNGLJD-UHFFFAOYSA-N ethyl(methyl)azanide;hafnium(4+) Chemical compound [Hf+4].CC[N-]C.CC[N-]C.CC[N-]C.CC[N-]C NPEOKFBCHNGLJD-UHFFFAOYSA-N 0.000 claims description 6
- 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 claims description 6
- 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 5
- 239000007983 Tris buffer Substances 0.000 claims description 5
- 229910052715 tantalum Inorganic materials 0.000 claims description 5
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 4
- 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 3
- 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 3
- LYWGPKCZWZCWAG-UHFFFAOYSA-N CCN=[Ta](N(C)C)(N(C)C)N(C)C Chemical compound CCN=[Ta](N(C)C)(N(C)C)N(C)C LYWGPKCZWZCWAG-UHFFFAOYSA-N 0.000 claims description 3
- ZLKUSFBEBZOVGX-UHFFFAOYSA-N CCN=[Ta](N(CC)CC)(N(CC)CC)N(CC)CC Chemical compound CCN=[Ta](N(CC)CC)(N(CC)CC)N(CC)CC ZLKUSFBEBZOVGX-UHFFFAOYSA-N 0.000 claims description 3
- ZZHXBZOWQPNBCA-UHFFFAOYSA-N N-(propan-2-ylamino)silylpropan-2-amine Chemical compound CC(C)N[SiH2]NC(C)C ZZHXBZOWQPNBCA-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- 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 3
- KCWYOFZQRFCIIE-UHFFFAOYSA-N ethylsilane Chemical compound CC[SiH3] KCWYOFZQRFCIIE-UHFFFAOYSA-N 0.000 claims description 3
- UGJHADISJBNSFP-UHFFFAOYSA-N n-bis(tert-butylamino)silyl-2-methylpropan-2-amine Chemical compound CC(C)(C)N[SiH](NC(C)(C)C)NC(C)(C)C UGJHADISJBNSFP-UHFFFAOYSA-N 0.000 claims description 3
- YYVGYULIMDRZMJ-UHFFFAOYSA-N propan-2-ylsilane Chemical compound CC(C)[SiH3] YYVGYULIMDRZMJ-UHFFFAOYSA-N 0.000 claims description 3
- HWEYZGSCHQNNEH-UHFFFAOYSA-N silicon tantalum Chemical group [Si].[Ta] HWEYZGSCHQNNEH-UHFFFAOYSA-N 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 claims description 3
- 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
- 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
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- MMMVJDFEFZDIIM-UHFFFAOYSA-N 2-$l^{1}-azanyl-2-methylpropane Chemical compound CC(C)(C)[N] MMMVJDFEFZDIIM-UHFFFAOYSA-N 0.000 claims 3
- FFXRCCZYEXDGRJ-UHFFFAOYSA-N n-bis(propan-2-ylamino)silylpropan-2-amine Chemical compound CC(C)N[SiH](NC(C)C)NC(C)C FFXRCCZYEXDGRJ-UHFFFAOYSA-N 0.000 claims 2
- MHMBUJVKUFAYFM-UHFFFAOYSA-N C(C)N(C)[Ta] Chemical compound C(C)N(C)[Ta] MHMBUJVKUFAYFM-UHFFFAOYSA-N 0.000 claims 1
- GMNCNDKLAZDHRJ-UHFFFAOYSA-N C(C)N(C)[W] Chemical compound C(C)N(C)[W] GMNCNDKLAZDHRJ-UHFFFAOYSA-N 0.000 claims 1
- AEKOOYWLWGERES-UHFFFAOYSA-N CCN=[Ta](N(C)CC)(N(C)CC)N(C)CC Chemical compound CCN=[Ta](N(C)CC)(N(C)CC)N(C)CC AEKOOYWLWGERES-UHFFFAOYSA-N 0.000 claims 1
- 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 1
- MXFQSOHUQAUGBO-UHFFFAOYSA-N CN(C)[W](=NC(C)(C)C)(=NC(C)(C)C)N(C)C.CCN(C)[Ta](=NC(C)(C)CC)(N(C)CC)N(C)CC Chemical compound CN(C)[W](=NC(C)(C)C)(=NC(C)(C)C)N(C)C.CCN(C)[Ta](=NC(C)(C)CC)(N(C)CC)N(C)CC MXFQSOHUQAUGBO-UHFFFAOYSA-N 0.000 claims 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 claims 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 claims 1
- WNUPENMBHHEARK-UHFFFAOYSA-N silicon tungsten Chemical group [Si].[W] WNUPENMBHHEARK-UHFFFAOYSA-N 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 36
- 229910052710 silicon Inorganic materials 0.000 abstract description 35
- 239000010703 silicon Substances 0.000 abstract description 34
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 32
- 230000015572 biosynthetic process Effects 0.000 abstract description 13
- 230000006872 improvement Effects 0.000 abstract description 3
- 150000004756 silanes Chemical class 0.000 abstract description 3
- 239000010408 film Substances 0.000 description 55
- 238000006243 chemical reaction Methods 0.000 description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- 239000010410 layer Substances 0.000 description 19
- 239000010936 titanium Substances 0.000 description 16
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 14
- 230000004888 barrier function Effects 0.000 description 11
- 239000000376 reactant Substances 0.000 description 11
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 9
- 239000004065 semiconductor Substances 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 238000009792 diffusion process Methods 0.000 description 7
- 239000002356 single layer Substances 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 150000004767 nitrides Chemical class 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- 239000005046 Chlorosilane Substances 0.000 description 3
- 229910007991 Si-N Inorganic materials 0.000 description 3
- 229910008051 Si-OH Inorganic materials 0.000 description 3
- 229910006294 Si—N Inorganic materials 0.000 description 3
- 229910006358 Si—OH Inorganic materials 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 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
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- 229910004200 TaSiN Inorganic materials 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 239000012686 silicon precursor Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 2
- CDEXIAPTXZWAOI-UHFFFAOYSA-N C(C)(C)(C)N=[W](N(CC)C)N(C)CC Chemical compound C(C)(C)(C)N=[W](N(CC)C)N(C)CC CDEXIAPTXZWAOI-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- KVKAPJGOOSOFDJ-UHFFFAOYSA-N CN(C)[Ta] Chemical compound CN(C)[Ta] KVKAPJGOOSOFDJ-UHFFFAOYSA-N 0.000 description 1
- ZLOKVAIRQVQRGC-UHFFFAOYSA-N CN(C)[Ti] Chemical compound CN(C)[Ti] ZLOKVAIRQVQRGC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910014299 N-Si Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- PDPJQWYGJJBYLF-UHFFFAOYSA-J hafnium tetrachloride Chemical compound Cl[Hf](Cl)(Cl)Cl PDPJQWYGJJBYLF-UHFFFAOYSA-J 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- TWVSWDVJBJKDAA-UHFFFAOYSA-N n-[bis(dimethylamino)silyl]-n-methylmethanamine Chemical compound CN(C)[SiH](N(C)C)N(C)C TWVSWDVJBJKDAA-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 238000001208 nuclear magnetic resonance pulse sequence Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/34—Nitrides
-
- A—HUMAN NECESSITIES
- A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
- A47G—HOUSEHOLD OR TABLE EQUIPMENT
- A47G33/00—Religious or ritual equipment in dwelling or for general use
-
- 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
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
- H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
- H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
- H01L21/0228—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition deposition by cyclic CVD, e.g. ALD, ALE, pulsed CVD
-
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Description
(R1NH)nSiR2 mH4-n-m(n=1、2;m=0、1、2;n+m≦3);及び
(R3 2N−NH)xSiR4 yH4-x-y(x=1、2;y=0、1、2;x+y≦3)
によって表されるモノアルキルアミノシラン及びヒドラジノシランであり、式中、R1-4が同じであるか又は異なり、アルキル、ビニル、アリル、フェニル、環状アルキル、フルオロアルキル、シリルアルキルからなる群より独立して選択される。
高品質の三成分金属ケイ素窒化物膜を製造できること;
重大な安全上及び腐食の問題がある通常の前駆体のうちの幾つかを除きつつ、高品質の膜を形成できること;
従来のプロセスよりも一般に低い温度、例えば、500℃よりも低い温度でTiN中に望ましいケイ素含量を組み込むことができること;
循環堆積法、例えば、CVD法においてケイ素源のパルス時間を制御することにより金属ケイ素窒化物中のケイ素含有量を制御できること;
循環CVDにおいて優れた堆積速度を達成することにより、生産規模でウェハ処理量の増加を可能にできること;
ALDを用いて超薄金属ケイ素窒化物膜を製造できること;
別の窒素源、例えば、アンモニアを使用することなく、2種の前駆体を用いて金属ケイ素窒化物膜を製造できること;
得られた金属ケイ素中の金属中心を低減することにより、得られた膜の抵抗率を低減できること;並びに
得られる金属ケイ素窒化物中に金属−窒素−ケイ素結合を形成することにより、膜の安定性を向上させることができること。
(R1NH)nSiR2 mH4-n-m(n=1、2;m=0、1、2;n+m≦3)
を有するモノアルキルアミノシランである。
(R3 2N−NH)xSiR4 yH4-x-y(x=1、2;y=0、1、2;x+y≦3)
を有するヒドラジノシランであり、ここで、モノアルキルアミノシランとヒドラジンにおけるR1-4は同じであるか又は異なり、アルキル、ビニル、アリル、フェニル、環状アルキル、フルオロアルキル、シリルアルキル及びアンモニアからなる群より独立して選択される。各化合物におけるアルキル官能性は、典型的には1〜10個の炭素原子を有するが、好ましい場合には1〜4個の炭素原子を有する。
1.金属アミドの蒸気を、反応又は堆積チャンバーに装填した加熱基材にさらし;
2.金属アミドを基材表面と反応させ;
3.未反応の金属アミドをパージし;
4.モノアルキルアミノシラン又はヒドラジノシランの蒸気を反応チャンバーに導入して吸収された金属アミドと反応させ;
5.未反応のモノアルキルアミノシラン又はヒドラジノシランをパージし;
6.必要に応じて、窒素含有反応体、例えば、アンモニアを反応チャンバーに導入し:
7.未反応の窒素含有反応体をパージし;そして
8.所望の膜厚に達するまで先に概説したサイクルを繰り返す。
[200℃でのTDMATとBTBASからのTiSiN膜の堆積]
シリコンウェハを堆積チャンバーに装入し、温度200℃及び圧力200Pa(1.5Torr)に維持する。2.6マイクロモルのTi含有化合物、テトラキス(ジメチルアミノ)チタン(TDMAT)を100sccmのN2とともに10秒間のパルスにわたってチャンバーに導入する。Tiアミドを堆積した後、未反応のTiアミドと副産物を2000sccmのN2で7.5秒間パージする。次いで、投与量4.73マイクロモルのSi含有化合物、ビス(tert−ブチルアミノ)シラン(BTBAS)を100sccmのN2とともに80秒間にわたって導入する。未反応のBTBASと副産物を2000sccmのN2で40秒間パージすることにより除去する。
[250℃でのTDMATとBTBASからのTiSiN膜のALD形成]
シリコンウェハを温度250℃及び圧力200Pa(1.5Torr)に維持すること以外は例1の手順に従う。2.6マイクロモルのTi含有化合物、テトラキス(ジメチルアミノ)チタン(TDMAT)を100sccmのN2とともに10秒間にわたってチャンバーに導入する。続いて2000sccmのN2で7.5秒間パージする。次いで、投与量4.73マイクロモルのSi含有化合物、ビス(tert−ブチルアミノ)シラン(BTBAS)を100sccmのN2とともに80秒間にわたって導入する。続いて2000sccmのN2で40秒間パージする。このサイクルを(4工程の)100サイクル繰り返し、144Å厚さの膜を生成した。
[TDMATとBTBASからのTiSiN膜の循環CVD形成]
シリコンウェハを温度300℃及び圧力200Pa(1.5Torr)に維持すること以外は例1の手順に従う。2.6マイクロモルのTi含有化合物、テトラキス(ジメチルアミノ)チタン(TDMAT)を100sccmのN2とともに10秒間にわたってチャンバーに導入する。続いて2000sccmのN2で7.5秒間パージする。次いで、投与量4.73マイクロモルのSi含有化合物、ビス(tert−ブチルアミノ)シラン(BTBAS)を100sccmのN2とともに80秒間にわたって導入する。続いて2000sccmのN2で40秒間パージする。これを(4工程の)100サイクル繰り返し、629Å厚さの膜を生成する。サイクル当たりの速度は6.29Åであり、このことは、この温度が高すぎてサイクル当たりの単層に堆積を制限できないことを示している。例1及び2とは対照的に、循環CVDのようなプロセスがこの温度で生じ、そのためにALD法よりもはるかに高い堆積速度になる。
[300℃でのBTBASのみを用いた循環CVD]
例3の手順に従う。投与量4.73マイクロモルのSi含有化合物、ビス(tert−ブチルアミノ)シラン(BTBAS)を100sccmのN2とともに80秒間にわたって導入する。続いて2000sccmのN2で40秒間パージする。これを(4工程の)100サイクル繰り返し、膜は生成せず、このことは、500℃よりも低い温度で窒化ケイ素のCVDを触媒するには吸収された金属アミドが必要であり、金属アミドが金属ケイ素窒化物の形成の際に重要な役割を果たすことを示している。
[300℃でのBTBASとアンモニアを用いた循環CVD]
例3の手順に従う。アンモニア(NH3)を100sccmのN2とともに10秒間にわたってチャンバーに導入する。続いて2000sccmのN2で7.5秒間パージする。次いで、投与量4.73マイクロモルのSi含有化合物、ビス(tert−ブチルアミノ)シラン(BTBAS)を100sccmのN2とともに80秒間にわたって導入する。続いて2000sccmのN2で40秒間パージする。これを(4工程の)100サイクル繰り返し、膜は生成しない。この例は、ビス(tert−ブチルアミノ)シラン(BTBAS)の分解を触媒して窒化ケイ素を形成するには吸収された金属アミドが必要であることを示している。
[350℃でのTBTDETとBTBASからのTaSiN膜のALD形成]
シリコンウェハを温度350℃及び圧力200Pa(1.5Torr)に維持すること以外は例1の手順に従う。1.1マイクロモルのTa含有化合物、tert−ブチルイミノトリス(ジエチルアミノ)タンタル(TBTDET)を50sccmのN2とともに20秒間にわたってチャンバーに導入する。続いて500sccmのN2で15秒間パージする。次いで、投与量4.73マイクロモルのSi含有化合物、ビス(tert−ブチルアミノ)シラン(BTBAS)を50sccmのN2とともに80秒間にわたって導入する。続いて500sccmのN2で40秒間パージする。これを(4工程の)200サイクル繰り返し、281Å厚さの膜を生成した。
[TBTDETとBTBASからのTaSiN膜の循環CVD形成]
シリコンウェハを温度400℃及び圧力200Pa(1.5Torr)に維持すること以外は例1の手順に従う。1.1マイクロモルのTa含有化合物、tert−ブチルイミノトリス(ジエチルアミノ)タンタル(TBTDET)を50sccmのN2とともに20秒間にわたってチャンバーに導入する。続いて500sccmのN2で15秒間パージする。次いで、投与量4.73マイクロモルのSi含有化合物、ビス(tert−ブチルアミノ)シラン(BTBAS)を50sccmのN2とともに80秒間にわたって導入する。続いて500sccmのN2で40秒間パージする。これを(4工程の)200サイクル繰り返し、2400Å厚さの膜を生成する。サイクル当たりの速度は12Åであり、このことは、この温度が高すぎてサイクル当たりの単層に堆積を制限できないことを示している。例6とは対照的に、循環CVDのようなプロセスがこの温度で生じ、そのためにALD法よりもはるかに高い堆積速度になる。
Claims (19)
- 基材上に金属ケイ素窒化物膜を形成するための循環堆積法であって、
金属アミドを堆積チャンバーに導入して加熱基材の表面と反応させる工程;
堆積チャンバーをパージして未反応の金属アミドと任意の副産物を除去する工程;
N−HフラグメントとSi−Hフラグメントを含有するケイ素化合物を堆積チャンバーに導入して前記反応された金属アミドと反応させる工程;
堆積チャンバーをパージして任意の未反応化合物と副産物を除去する工程;及び
所望の膜厚が確立されるまで循環堆積法を繰り返す工程
を含む、循環堆積法。 - 前記金属アミドが、テトラキス(ジメチルアミノ)チタン(TDMAT)、テトラキス(ジエチルアミノ)チタン(TDEAT)、テトラキス(エチルメチルアミノ)チタン(TEMAT)、テトラキス(ジメチルアミノ)ジルコニウム(TDMAZ)、テトラキス(ジエチルアミノ)ジルコニウム(TDEAZ)、テトラキス(エチルメチルアミノ)ジルコニウム(TEMAZ)、テトラキス(ジメチルアミノ)ハフニウム(TDMAH)、テトラキス(ジエチルアミノ)ハフニウム(TDEAH)、テトラキス(エチルメチルアミノ)ハフニウム(TEMAH)、tert−ブチルイミノトリス(ジエチルアミノ)タンタル(TBTDET)、tert−ブチルイミノトリス(ジメチルアミノ)タンタル(TBTDMT)、tert−ブチルイミノトリス(エチルメチルアミノ)タンタル(TBTEMT)、エチルイミノトリス(ジエチルアミノ)タンタル(EITDET)、エチルイミノトリス(ジメチルアミノ)タンタル(EITDMT)、エチルイミノトリス(エチルメチルアミノ)タンタル(EITEMT)、tert−アミルイミノトリス(ジメチルアミノ)タンタル(TAIMAT)、tert−アミルイミノトリス(ジエチルアミノ)タンタル、ペンタキス(ジメチルアミノ)タンタル、tert−アミルイミノトリス(エチルメチルアミノ)タンタル、ビス(tert−ブチルイミノ)ビス(ジメチルアミノ)タングステン(BTBMW)、ビス(tert−ブチルイミノ)ビス(ジエチルアミノ)タングステン、ビス(tert−ブチルイミノ)ビス(エチルメチルアミノ)タングステン及びそれらの混合物からなる群より選択される、請求項1に記載の循環堆積法。
- N−HフラグメントとSi−Hフラグメントの両方を含有する前記ケイ素化合物が、以下の式、即ち、
(R1NH)nSiR2 mH4-n-m(n=1、2;m=0、1、2;n+m≦3)を有するモノアルキルアミノシランと;
以下の式、即ち、
(R3 2N−NH)xSiR4 yH4-x-y(x=1、2;y=0、1、2;x+y≦3)を有するヒドラジノシランからなる群より選択され、
式中、R1-4が同じであるか又は異なり、アルキル、ビニル、アリル、フェニル、環状アルキル、フルオロアルキル、シリルアルキルからなる群より独立して選択される、請求項2に記載の循環堆積法。 - 前記金属ケイ素窒化物がチタンケイ素窒化物である、請求項3に記載の循環堆積法。
- 前記金属アミドが、テトラキス(ジメチルアミノ)チタン(TDMAT)、テトラキス(ジエチルアミノ)チタン(TDEAT)、テトラキス(エチルメチルアミノ)チタン(TEMAT)からなる群より選択される、請求項3に記載の循環堆積法。
- N−HフラグメントとSi−Hフラグメントを含有する前記ケイ素化合物が、ビス(tert−ブチルアミノ)シラン(BTBAS)、トリス(tert−ブチルアミノ)シラン、ビス(イソ−プロピルアミノ)シラン、トリス(イソ−プロピルアミノ)シラン、ビス(1,1−ジメチルヒドラジノ)シラン、トリス(1,1−ジメチルヒドラジノ)シラン、ビス(1,1−ジメチルヒドラジノ)エチルシラン、ビス(1,1−ジメチルヒドラジノ)イソプロピルシラン、ビス(1,1−ジメチルヒドラジノ)ビニルシランからなる群より選択される、請求項4に記載の循環堆積法。
- 前記金属ケイ素窒化物がタンタルケイ素窒化物である、請求項3に記載の循環堆積法。
- 前記金属ケイ素窒化物がタングステンケイ素窒化物である、請求項3に記載の循環堆積法。
- 前記循環堆積法が循環化学気相成長法である、請求項3に記載の循環堆積法。
- 前記循環堆積法が原子層堆積法である、請求項3に記載の循環堆積法。
- 前記堆積チャンバーの圧力が50mtorr〜100torrであり、当該堆積チャンバーの温度が500℃よりも低い、請求項3に記載の循環堆積法。
- アンモニアが第3の前駆体として用いられ、添加の順序が、金属アミド−アンモニア−モノアルキルアミノシラン及び金属アミド−モノアルキルアミノシラン−アンモニアからなる群より選択される、請求項11に記載の循環堆積法。
- 複数の前駆体が堆積チャンバーに逐次的に導入され、気化され、そして三成分金属ケイ素窒化物膜を形成するための条件下で基材上に堆積される三成分金属ケイ素窒化物膜を形成するための改善された循環堆積法であって、
金属アミドを前駆体として使用すること;
NH及びSiHフラグメントを有するケイ素化合物を前駆体として使用すること;及び
窒素含有ガスを前駆体として使用すること
を含み、金属アミド、NH及びSiHフラグメントを有するケイ素化合物、及び窒素含有ガスが堆積チャンバーに逐次的に導入される、循環堆積法。 - 前記堆積チャンバーの圧力が50mtorr〜100torrであり、当該堆積チャンバーの温度が約200〜350℃である、請求項13に記載の循環堆積法。
- 前記金属アミドが前記ケイ素化合物の前に堆積され、当該金属アミドが、テトラキス(ジメチルアミノ)チタン(TDMAT)、テトラキス(ジエチルアミノ)チタン(TDEAT)、テトラキス(エチルメチルアミノ)チタン(TEMAT)、テトラキス(ジメチルアミノ)ジルコニウム(TDMAZ)、テトラキス(ジエチルアミノ)ジルコニウム(TDEAZ)、テトラキス(エチルメチルアミノ)ジルコニウム(TEMAZ)、テトラキス(ジメチルアミノ)ハフニウム(TDMAH)、テトラキス(ジエチルアミノ)ハフニウム(TDEAH)、テトラキス(エチルメチルアミノ)ハフニウム(TEMAH)、tert−ブチルイミノトリス(ジエチルアミノ)タンタル(TBTDET)、tert−ブチルイミノトリス(ジメチルアミノ)タンタル(TBTDMT)、tert−ブチルイミノトリス(エチルメチルアミノ)タンタル(TBTEMT)、エチルイミノトリス(ジエチルアミノ)タンタル(EITDET)、エチルイミノトリス(ジメチルアミノ)タンタル(EITDMT)、エチルイミノトリス(エチルメチルアミノ)タンタル(EITEMT)、tert−アミルイミノトリス(ジメチルアミノ)タンタル(TAIMAT)、tert−アミルイミノトリス(ジエチルアミノ)タンタル、ペンタキス(ジメチルアミノ)タンタル、tert−アミルイミノトリス(エチルメチルアミノ)タンタル、ビス(tert−ブチルイミノ)ビス(ジメチルアミノ)タングステン(BTBMW)、ビス(tert−ブチルイミノ)ビス(ジエチルアミノ)タングステン、ビス(tert−ブチルイミノ)ビス(エチルメチルアミノ)タングステンからなる群より選択される、請求項13に記載の循環堆積法。
- N−HフラグメントとSi−Hフラグメントを含有する前記ケイ素化合物が、ビス(tert−ブチルアミノ)シラン(BTBAS)、トリス(tert−ブチルアミノ)シラン、ビス(イソ−プロピルアミノ)シラン、トリス(イソ−プロピルアミノ)シラン、ビス(1,1−ジメチルヒドラジノ)シラン、トリス(1,1−ジメチルヒドラジノ)シラン、ビス(1,1−ジメチルヒドラジノ)エチルシラン、ビス(1,1−ジメチルヒドラジノ)イソプロピルシラン、ビス(1,1−ジメチルヒドラジノ)ビニルシランからなる群より選択される、請求項13に記載の循環堆積法。
- 各前駆体を導入した後、パージガスが前記堆積チャンバーに通される、請求項13に記載の循環堆積法。
- 前記窒素含有ガスが、アンモニア、ヒドラジン、アルキルヒドラジン及びジアルキルヒドラジンからなる群より選択される、請求項13に記載の循環堆積法。
- 前記金属アミドが最初に導入され、続いて前記窒素含有ガス、次いで前記ケイ素化合物が導入されるか、又は前記金属アミドが最初に導入され、続いて前記ケイ素化合物、次いで前記窒素含有ガスが導入され、所望の膜厚が確立されるまで循環堆積法が繰り返される、請求項13に記載の循環堆積法。
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CN100537842C (zh) | 2009-09-09 |
ATE421166T1 (de) | 2009-01-15 |
TWI265207B (en) | 2006-11-01 |
US20060182885A1 (en) | 2006-08-17 |
JP2006225764A (ja) | 2006-08-31 |
EP1691400A1 (en) | 2006-08-16 |
KR20060091240A (ko) | 2006-08-18 |
EP1691400B1 (en) | 2009-01-14 |
TW200628628A (en) | 2006-08-16 |
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