KR20220011093A - 몰리브덴층을 증착하기 위한 방법 및 시스템 - Google Patents
몰리브덴층을 증착하기 위한 방법 및 시스템 Download PDFInfo
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- KR20220011093A KR20220011093A KR1020210092540A KR20210092540A KR20220011093A KR 20220011093 A KR20220011093 A KR 20220011093A KR 1020210092540 A KR1020210092540 A KR 1020210092540A KR 20210092540 A KR20210092540 A KR 20210092540A KR 20220011093 A KR20220011093 A KR 20220011093A
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- molybdenum
- transition metal
- precursor
- reaction chamber
- reactant
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- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 104
- 239000011733 molybdenum Substances 0.000 title claims abstract description 104
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 238000000034 method Methods 0.000 title claims abstract description 96
- 238000000151 deposition Methods 0.000 title description 22
- 239000000758 substrate Substances 0.000 claims abstract description 43
- 230000008021 deposition Effects 0.000 claims abstract description 21
- 239000002243 precursor Substances 0.000 claims description 72
- 239000000376 reactant Substances 0.000 claims description 71
- 238000006243 chemical reaction Methods 0.000 claims description 67
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 60
- 229910052723 transition metal Inorganic materials 0.000 claims description 43
- -1 transition metal sulfide Chemical class 0.000 claims description 34
- 150000003624 transition metals Chemical class 0.000 claims description 30
- 229910052757 nitrogen Inorganic materials 0.000 claims description 29
- 230000000737 periodic effect Effects 0.000 claims description 27
- 238000005137 deposition process Methods 0.000 claims description 21
- 229910052717 sulfur Inorganic materials 0.000 claims description 20
- 239000011593 sulfur Substances 0.000 claims description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 16
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 230000009467 reduction Effects 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 150000004820 halides Chemical class 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 239000003446 ligand Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 4
- 230000004888 barrier function Effects 0.000 claims description 4
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 150000002431 hydrogen Chemical group 0.000 claims description 3
- WSWMGHRLUYADNA-UHFFFAOYSA-N 7-nitro-1,2,3,4-tetrahydroquinoline Chemical compound C1CCNC2=CC([N+](=O)[O-])=CC=C21 WSWMGHRLUYADNA-UHFFFAOYSA-N 0.000 claims description 2
- JYLUAHPKLGKVNL-UHFFFAOYSA-J C1(C=CC=C1)[Mo](Cl)(Cl)(Cl)Cl Chemical compound C1(C=CC=C1)[Mo](Cl)(Cl)(Cl)Cl JYLUAHPKLGKVNL-UHFFFAOYSA-J 0.000 claims description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical group S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- 229910015275 MoF 6 Inorganic materials 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 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
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 229910000085 borane Inorganic materials 0.000 claims description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 2
- DBGPLCIFYUHWKA-UHFFFAOYSA-H hexachloromolybdenum Chemical compound Cl[Mo](Cl)(Cl)(Cl)(Cl)Cl DBGPLCIFYUHWKA-UHFFFAOYSA-H 0.000 claims description 2
- 150000002429 hydrazines Chemical class 0.000 claims description 2
- GICWIDZXWJGTCI-UHFFFAOYSA-I molybdenum pentachloride Chemical compound Cl[Mo](Cl)(Cl)(Cl)Cl GICWIDZXWJGTCI-UHFFFAOYSA-I 0.000 claims description 2
- OYMJNIHGVDEDFX-UHFFFAOYSA-J molybdenum tetrachloride Chemical compound Cl[Mo](Cl)(Cl)Cl OYMJNIHGVDEDFX-UHFFFAOYSA-J 0.000 claims description 2
- ZSSVQAGPXAAOPV-UHFFFAOYSA-K molybdenum trichloride Chemical group Cl[Mo](Cl)Cl ZSSVQAGPXAAOPV-UHFFFAOYSA-K 0.000 claims description 2
- 150000002831 nitrogen free-radicals Chemical class 0.000 claims description 2
- SFPKXFFNQYDGAH-UHFFFAOYSA-N oxomolybdenum;tetrahydrochloride Chemical compound Cl.Cl.Cl.Cl.[Mo]=O SFPKXFFNQYDGAH-UHFFFAOYSA-N 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- 150000003573 thiols Chemical class 0.000 claims description 2
- 230000007704 transition Effects 0.000 claims description 2
- LYGRUQGJJFJQCK-UHFFFAOYSA-K trichloridooxidomolybdenum Chemical compound Cl[Mo](Cl)(Cl)=O LYGRUQGJJFJQCK-UHFFFAOYSA-K 0.000 claims description 2
- 230000006911 nucleation Effects 0.000 abstract description 2
- 238000010899 nucleation Methods 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 44
- 230000008569 process Effects 0.000 description 44
- 239000000463 material Substances 0.000 description 26
- 238000000231 atomic layer deposition Methods 0.000 description 14
- 238000010926 purge Methods 0.000 description 10
- 238000006722 reduction reaction Methods 0.000 description 10
- 239000000460 chlorine Substances 0.000 description 8
- 239000004065 semiconductor Substances 0.000 description 7
- 239000011261 inert gas Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 229910052794 bromium Inorganic materials 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 5
- 210000002381 plasma Anatomy 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000012159 carrier gas Substances 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 239000003989 dielectric material Substances 0.000 description 3
- 229910052735 hafnium Inorganic materials 0.000 description 3
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 229910000078 germane Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000001451 molecular beam epitaxy Methods 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910004129 HfSiO Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- DGDBSLKLKZTDSL-UHFFFAOYSA-N [I].[Mo] Chemical compound [I].[Mo] DGDBSLKLKZTDSL-UHFFFAOYSA-N 0.000 description 1
- GTVGLPJVORBGRY-UHFFFAOYSA-N [Mo].BrOBr Chemical compound [Mo].BrOBr GTVGLPJVORBGRY-UHFFFAOYSA-N 0.000 description 1
- 150000001356 alkyl thiols Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000001504 aryl thiols Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000000277 atomic layer chemical vapour deposition Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 150000001723 carbon free-radicals Chemical class 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000004871 chemical beam epitaxy Methods 0.000 description 1
- CNRRZWMERIANGJ-UHFFFAOYSA-N chloro hypochlorite;molybdenum Chemical compound [Mo].ClOCl CNRRZWMERIANGJ-UHFFFAOYSA-N 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- HXHQDHKWCRUPKS-UHFFFAOYSA-N fluoro hypofluorite molybdenum Chemical compound [Mo].FOF HXHQDHKWCRUPKS-UHFFFAOYSA-N 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 238000000171 gas-source molecular beam epitaxy Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(iv) oxide Chemical compound O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- MDKDXDROOSZTMM-UHFFFAOYSA-N iodo hypoiodite molybdenum Chemical compound [Mo].IOI MDKDXDROOSZTMM-UHFFFAOYSA-N 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- LNDHQUDDOUZKQV-UHFFFAOYSA-J molybdenum tetrafluoride Chemical compound F[Mo](F)(F)F LNDHQUDDOUZKQV-UHFFFAOYSA-J 0.000 description 1
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 238000001208 nuclear magnetic resonance pulse sequence Methods 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- YPFBRNLUIFQCQL-UHFFFAOYSA-K tribromomolybdenum Chemical compound Br[Mo](Br)Br YPFBRNLUIFQCQL-UHFFFAOYSA-K 0.000 description 1
- 238000005019 vapor deposition process Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
-
- 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
- C23C16/08—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 halides
- C23C16/14—Deposition of only one other metal element
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- 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
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
- H01L21/76841—Barrier, adhesion or liner layers
- H01L21/76843—Barrier, adhesion or liner layers formed in openings in a dielectric
- H01L21/76846—Layer combinations
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/02—Pretreatment of the material to be coated
- C23C16/0272—Deposition of sub-layers, e.g. to promote the adhesion of the main coating
-
- 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
-
- 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
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Abstract
기판의 표면 상에 몰리브덴층들을 형성하기 위한 방법들 및 시스템들 및 상기 방법들을 사용하여 형성된 구조물들 및 소자들이 개시된다. 예시적인 방법들은 몰리브덴층을 형성하기 전에 하부층을 형성하는 단계를 포함한다. 상기 하부층은 상기 몰리브덴층 내의 응력을 조작하고 및/또는 상기 몰리브덴층을 형성하는 단계의 핵생성 온도 및/또는 증착 온도를 감소시키는데 사용될 수 있다.
Description
본 개시는 일반적으로 기판의 표면 상에 층을 형성하기에 적합한 방법 및 시스템, 및 상기 층을 포함하는 구조체에 관한 것이다. 보다 구체적으로, 본 개시는 몰리브덴을 포함하는 층을 형성하기 위한 방법 및 시스템, 및 상기 방법 및 시스템을 사용하여 형성된 구조체에 관한 것이다.
반도체 소자와 같은 전자 장치의 스케일링은 집적 회로의 성능 및 밀도를 상당히 개선시켰다. 그러나, 종래의 소자 스케일링 기술은 미래의 기술 분기점에서 큰 도전에 직면해 있다.
예를 들어, 하나의 도전 과제는, 원하는 유효 비저항, 낮은 증착 온도, 및/또는 성능(예를 들어, 막 응력) 튜닝성과 같은 원하는 특성을 나타내는, 금속 갭 필(gap fill) 적용, 라이너 적용 등에 사용하기에 적절한 전도성 재료를 찾는 것이었다. 따라서, 하나 이상의 이러한 특성을 갖는 금속층을 형성하기 위한 개선된 방법 및 시스템이 요구된다.
이 부분에 진술된 문제점 및 해결책을 포함한 임의의 논의는, 단지 본 개시에 대한 맥락을 제공하는 목적으로만 본 개시에 포함되었다. 이러한 논의는 임의의 또는 모든 정보가 본 발명이 만들어졌거나 그렇지 않으면 선행 기술을 구성하는 시점에 알려진 것으로 간주되어서는 안된다.
본 발명의 내용은 개념의 선택을 단순화된 형태로 도입하며, 이는 이하에서 더욱 상세히 설명될 수 있다. 본 발명의 내용은 청구된 요지의 주된 특징 또는 본질적인 특징을 필수적으로 구분하려는 의도가 아니며 청구된 요지의 범주를 제한하기 위해 사용하려는 의도 또한 아니다.
본 개시의 다양한 구현예는, 몰리브덴층을 포함한 구조체를 형성하는 방법, 이러한 방법을 사용하여 형성된 구조체, 그리고 상기 방법을 수행하기 위한 및/또는 상기 구조체를 형성하기 위한 시스템에 관한 것이다. 몰리브덴층은, 라이너 또는 배리어 층(예를 들어, 3D-NAND 또는 DRAM 워드-라인) 응용예, 상호접속 응용예 등으로 사용하기 위한, 갭 필(예를 들어, 상보적 금속 산화물 반도체(CMOS)) 응용을 포함하는 다양한 응용에 사용될 수 있다. 또한, 이하에서 더욱 상세히 설명되는 바와 같이, 본 개시의 예는 몰리브덴층을 증착하기 위한 전통적인 기술에 비해, 상대적으로 낮은 온도에서 몰리브덴층을 증착하는 데 사용될 수 있다.
본 개시의 예시적인 구현예에 따라, 구조체를 형성하는 방법이 개시된다. 구조체를 형성하는 예시적인 방법은 기판을 제공하는 단계, 기판의 표면 상에 전이금속 황화물, 전이금속 탄화물, 및 전이금속 질화물 중 하나 이상을 포함하는 하부층을 형성하는 단계, 및 하부층 위에 놓이는 몰리브덴층을 형성하는 단계를 포함한다. 전이 금속은, 예를 들어, 티타늄, 텅스텐, 몰리브덴, 바나듐, 니오븀, 탄탈륨, 코발트, 하프늄, 및 지르코늄으로 이루어진 군으로부터 선택되는, 4족 내지 7족 전이 금속일 수 있다. 본 개시의 예에 따르면, 하부층의 두께는 0nm 초과 및 10nm 미만, 약 1-10nm, 약 1-5nm, 또는 5nm 초과 및 10nm 미만이다. 추가적인 예에 따르면, 하부층을 형성하는 단계는 주기적 증착 공정을 포함한다. 주기적 증착 공정은, 전이 금속 전구체를 반응 챔버에 제공하는 단계, 탄소, 황, 및 질소 반응물 중 하나 이상을 반응 챔버에 제공하는 단계, 및 환원 반응물을 반응 챔버에 제공하는 단계를 포함할 수 있다. 몰리브덴층을 형성하는 단계는 주기적 증착 공정을 포함할 수 있다. 하부층을 형성하는 단계 및/또는 몰리브덴층을 형성하는 단계 동안의 온도는 650℃ 미만, 600℃ 미만, 550℃ 미만, 500℃ 미만, 약 300℃ 내지 600℃, 약 300℃ 내지 650℃, 약 300℃ 내지 550℃, 약 300℃ 내지 500℃, 또는 약 300℃ 내지 450℃일 수 있다. 일부 경우에, 하부층을 형성하는 단계 동안 기판의 온도는 몰리브덴층을 형성하는 단계 동안 온도보다 작을 수 있다. 몰리브덴층을 형성하는 단계 동안 반응 챔버 내의 압력은 760토르(Torr) 미만, 약 0.2 내지 약 300토르, 약 0.5 내지 약 60토르, 또는 약 20 내지 약 80토르일 수 있다. 하부층을 형성하는 단계 동안 반응 챔버 내의 압력은 약 1 내지 약 760토르, 약 0.2 내지 약 300토르, 약 0.5 내지 약 50토르, 또는 약 0.5 내지 약 20토르일 수 있다. 하부층을 형성하는 단계 동안 반응 챔버 내의 압력은 몰리브덴층을 형성하는 단계 동안 압력보다 작을 수 있으며, 예를 들어 위에서 지정된 범위 이내일 수 있다.
본 개시의 추가 예시적인 구현예에 따라, 구조는 본원에 설명된 방법을 사용하여 형성된다. 구조체는 기판, 기판 위에 놓여 형성된 하부층, 및 하부층 위에 놓여 형성된 몰리브덴층을 포함할 수 있다. 하부층은 후속하여 형성된 몰리브덴층 내의 응력을 조작하고/하거나 몰리브덴층의 핵생성을 강화하고, 이에 의해 하부층 위에 놓이는 몰리브덴층을 형성하는 단계 동안 사용되는 증착 온도(예를 들어, 기판의 온도)를 감소시키기 위해 사용될 수 있다. 몰리브덴층은, 라이너 또는 배리어, 상호접속 등으로서, 갭 필을 포함하는 다양한 응용예에 사용될 수 있다.
본 개시의 보다 추가적인 예에 따라, 본원에 설명된 방법을 수행하고/수행하거나 구조체, 또는 이들 중 일부를 형성하기 위한 시스템이 개시되어 있다.
이들 및 다른 구현예는 첨부된 도면을 참조하는 특정 구현예의 다음 상세한 설명으로부터 당업자에게 쉽게 분명해질 것이다. 본 발명은 개시된 임의의 특정 구현예에 한정되지 않는다.
다음의 예시적인 도면과 연관하여 고려되는 경우에 발명의 상세한 설명 및 청구범위를 참조함으로써, 본 개시의 구현예에 대해 더욱 완전한 이해를 얻을 수 있다.
도 1은 본 개시의 예시적 구현예에 따른 방법을 나타낸다.
도 2는 본 개시의 예시적 구현예에 따른 공정을 나타낸다.
도 3은 본 개시의 예시적 구현예에 따른 공정을 나타낸다.
도 4는 본 개시의 예에 따른 구조체를 나타낸다.
도 5는 본 개시의 예시적인 추가 구현예에 따른 반응기 시스템을 나타낸다.
도 6 내지 도 8은 본 개시의 실시예에 따라 형성된 막 및 구조체에서의 몰리브덴 막 응력을 도시한다.
도면의 요소는 간략하고 명료하게 도시되어 있으며, 반드시 축적대로 도시되지 않았음을 이해할 것이다. 예를 들어, 본 개시에서 예시된 구현예의 이해를 돕기 위해 도면 중 일부 구성 요소의 치수는 다른 구성 요소에 비해 과장될 수 있다.
도 1은 본 개시의 예시적 구현예에 따른 방법을 나타낸다.
도 2는 본 개시의 예시적 구현예에 따른 공정을 나타낸다.
도 3은 본 개시의 예시적 구현예에 따른 공정을 나타낸다.
도 4는 본 개시의 예에 따른 구조체를 나타낸다.
도 5는 본 개시의 예시적인 추가 구현예에 따른 반응기 시스템을 나타낸다.
도 6 내지 도 8은 본 개시의 실시예에 따라 형성된 막 및 구조체에서의 몰리브덴 막 응력을 도시한다.
도면의 요소는 간략하고 명료하게 도시되어 있으며, 반드시 축적대로 도시되지 않았음을 이해할 것이다. 예를 들어, 본 개시에서 예시된 구현예의 이해를 돕기 위해 도면 중 일부 구성 요소의 치수는 다른 구성 요소에 비해 과장될 수 있다.
아래에 제공된 방법, 구조체, 소자 및 시스템의 예시적인 구현예의 설명은 단지 예시적인 것이고, 예시의 목적으로만 의도된 것이며, 다음의 설명은 본 개시의 범주 또는 청구 범위를 제한하고자 함이 아니다. 또한, 특징부를 기술한 다수 구현예를 인용하는 것이 추가적인 특징부를 갖는 다른 구현예 또는 명시된 특징부의 다른 조합을 포함한 다른 구현예를 배제하고자 함이 아니다. 예를 들어, 다양한 구현예가 예시적인 구현예로서 제시되고, 종속된 청구범위에 인용될 수 있다. 달리 언급되지 않는 한, 예시적인 구현예 또는 이의 구성 요소는 다양한 조합으로 조합될 수 있거나 서로 분리되어 적용될 수 있다.
이하에서 더욱 상세히 설명되는 바와 같이, 본 개시의 다양한 구현예는 다양한 응용예에 적합한 구조를 형성하기 위한 방법을 제공한다. 예시적인 방법은, 예를 들어 몰리브덴층, 적절한 갭 필 적용, 상호접속 적용, 배리어 또는 라이너 적용 등을 형성하는 데 사용될 수 있다. 그러나, 달리 언급되지 않는 한, 본 발명은 반드시 이러한 예시로 제한되지는 않는다.
본 개시에서, "가스"는 정상 온도 및 압력(NTP)에서 가스, 증기화된 고체 및/또는 증기화된 액체인 재료를 포함할 수 있으며, 맥락에 따라 단일 가스 또는 가스 혼합물로 구성될 수 있다. 공정 가스 이외의 가스, 즉 가스 분배 어셈블리, 다른 가스 분배 장치 등을 통과하지 않고 유입되는 가스는, 예를 들어 반응 공간을 밀폐하기 위해 사용될 수 있고, 희귀 가스와 같은 밀폐 가스를 포함할 수 있다. 일부 경우에서, 용어 "전구체"는 다른 화합물을 생성하는 화학 반응에 참여하는 화합물, 및 특히 막 매트릭스 또는 막의 메인 골격을 구성하는 화합물을 지칭할 수 있으며; 용어 "반응물"은 용어 전구체와 상호 교환적으로 사용될 수 있다. 용어 "불활성 가스"는 화학 반응에 참여하지 않고/않거나 상당한 정도로 막 매트릭스의 일부가 되지 않는 가스를 지칭할 수 있다. 예시적인 불활성 가스는 헬륨, 아르곤, 및 이들의 임의의 조합을 포함한다. 일부 경우에, 불활성 가스는 질소 및/또는 수소를 포함할 수 있다.
본원에서 사용되는 바와 같이, 용어 "기판"은, 형성하기 위해 사용될 수 있는, 또는 그 위에 소자, 회로, 또는 막이 형성될 수 있는, 임의의 하부 재료 또는 재료들을 지칭할 수 있다. 기판은 실리콘(예, 단결정 실리콘), 게르마늄과 같은 다른 IV족 재료, 또는 II-VI족 또는 III-V족 반도체 재료와 같은 다른 반도체 재료와 같은 벌크 재료를 포함할 수 있고, 벌크 재료 위에 놓이거나 그 아래에 놓인 하나 이상의 층을 포함할 수 있다. 또한, 기판은, 기판의 층의 적어도 일부 내에 또는 그 위에 형성된 다양한 특징부, 예컨대 오목부, 돌출부 등을 포함할 수 있다. 예로서, 기판은 벌크 반도체 재료, 및 상기 벌크 반도체 재료의 적어도 일부분 위에 놓인 절연 또는 유전체 재료 층을 포함할 수 있다.
본원에서 사용되는 바와 같이, 용어 "막" 및/또는 "층"은 본원에 개시된 방법에 의해 증착된 재료와 같이 임의의 연속적인 또는 비연속적인 구조 및 재료를 지칭할 수 있다. 예를 들어, 막 및/또는 층은 이차원 재료, 삼차원 재료, 나노입자 또는 심지어는 부분 또는 전체 분자층 또는 부분 또는 전체 원자층 또는 원자 및/또는 분자 클러스터를 포함할 수 있다. 막 또는 층은 핀홀을 갖는 재료 또는 층을 포함할 수 있고, 이는 적어도 부분적으로 연속적일 수 있다.
본원에서 사용되는 바와 같이, "구조체"는 본원에 기술된 바와 같은 기판일 수 있거나 이를 포함할 수 있다. 구조체는, 기판 위에 놓이는 하나 이상의 층, 예컨대 본원에서 설명된 방법에 따라 형성된 하나 이상의 층을 포함할 수 있다.
용어 "주기적 증착 공정" 또는 "순환 증착 공정"은 반응 챔버 내로 전구체(및/또는 반응물)를 순차적으로 도입시켜 기판 위에 층을 증착하는 것을 지칭할 수 있으며 원자층 증착(ALD) 및 주기적 화학 기상 증착(주기적 CVD), 및 ALD 성분과 주기적 CVD 성분을 포함한 하이브리드 주기적 증착 공정과 같은 처리 기술을 포함한다. 용어 방법 및 공정은 상호 교환적으로 사용될 수 있다.
용어 "원자층 증착"은 기상 증착 공정을 지칭할 수 있고, 여기서 증착 사이클, 전형적으로 복수의 연속 증착 사이클은 공정 챔버에서 수행된다. 본원에서 사용된 용어 원자층 증착은, 전구체(들)/반응 가스(들), 및 퍼지(예, 불활성 캐리어) 가스(들)의 교번 펄스로 수행되는 경우, 화학 기상 원자층 증착, 원자층 에피택시(ALE), 분자 빔 에피택시(MBE), 가스 공급원 MBE, 또는 유기금속 MBE, 및 화학적 빔 에피택시와 같은 관련 용어들에 의해 지정된 공정을 포함하는 것을 또한 의미한다.
일반적으로, ALD 공정의 경우, 각각의 사이클 중에 전구체는 반응 챔버에 도입되고 증착 표면(예, 이전 ALD 사이클로부터 이전에 증착된 재료 또는 다른 재료를 포함할 수 있는 기판 표면)에 화학 흡착되고, 추가적인 전구체와 쉽게 반응하지 않는(즉, 자기 제한적 반응인) 단층 또는 서브 단층을 형성한다. 그 후, 일부 경우에서, 반응물(예, 다른 전구체 또는 반응 가스)을 후속해서 공정 챔버에 도입시켜 증착 표면 상에서 화학 흡착된 전구체를 원하는 재료로 전환시키는 데 사용한다. 반응물은 전구체와 더 반응할 수 있다. 하나 이상의 사이클 동안, 예를 들어 각 사이클의 각 단계 중에 퍼지 단계를 사용하여, 공정 챔버로부터 과잉의 전구체를 제거하고/제거하거나, 공정 챔버로부터 과잉의 반응물 및/또는 반응 부산물을 제거할 수 있다.
본원에서 사용되는 바와 같이, "몰리브덴층"은 금속 몰리브덴과 같은, 몰리브덴을 포함하는 화학식으로 나타낼 수 있는 재료 층일 수 있다.
본원에서 사용되는 바와 같이, "몰리브덴 전구체"는, 가스 또는 기체가 될 수 있고 몰리브덴을 포함하는 화학식으로 나타낼 수 있는 재료를 포함한다.
본원에서 사용되는 바와 같이, "몰리브덴 할라이드 전구체"는, 가스 또는 기체가 될 수 있고 몰리브덴 및 할로겐, 예컨대 불소(F), 염소(Cl), 브롬(Br), 및 요오드(I) 중 하나 이상을 포함한 화학식으로 나타낼 수 있는 재료를 포함한다.
용어 "질소 반응물"은, 가스가 될 수 있고 질소를 포함한 화학식으로 표현될 수 있는 가스 또는 재료를 지칭할 수 있다. 일부 경우에, 화학식은 질소 및 수소를 포함한다. 일부 경우에, 질소 반응물은 이원자 질소를 포함하지 않는다.
용어 "황 반응물"은, 가스가 될 수 있고 황을 포함한 화학식으로 표시될 수 있는 가스 또는 재료를 지칭할 수 있다. 일부 경우에, 화학식은 황 및 수소를 포함한다. 일부 경우에, 황 반응물은 황 원자를 포함하지 않는다.
용어 "탄소 반응물"은, 가스가 될 수 있고 탄소를 포함한 화학식으로 표시될 수 있는 가스 또는 재료를 지칭할 수 있다. 일부 경우에, 화학식은 탄소 및 수소를 포함한다.
또한, 본 개시에서, 변수의 임의의 두 수치가 상기 변수의 실행 가능한 범위를 구성할 수 있고, 표시된 임의의 범위는 끝점을 포함하거나 배제할 수 있다. 추가적으로, 지시된 변수의 임의의 값은 ("약"으로 표시되는지의 여부에 관계없이) 정확한 값 또는 대략적인 값을 지칭할 수 있고 등가를 포함할 수 있으며, 평균, 중간, 대표, 다수 등을 지칭할 수 있다. 또한, 본 개시에서, 용어 "포함한", "의해 구성되는", 및 "갖는"은 일부 구현예에서 "통상적으로 또는 대략적으로 포함하는", "포함하는", "본질적으로 이루어지는", 또는 "이루어지는"을 독립적으로 지칭한다. 본 개시에서, 임의의 정의된 의미는 일부 구현예에서 반드시 보통의 그리고 관습적인 의미를 배제하는 것은 아니다.
이제 도 1로 돌아가서, 도 1은 본 개시의 예시적인 구현예에 따른 구조체를 형성하는 방법(100)을 도시한다. 방법(100)은, 기판을 제공하는 단계(단계 102), 하부층을 형성하는 단계(단계 104), 및 몰리브덴층을 형성하는 단계(단계 106)를 포함한다.
단계(102) 동안에, 반응 챔버 내에 기판을 제공한다. 단계(102) 중에 사용된 반응 챔버는, 주기적 증착 공정을 수행하도록 구성된 화학 기상 증착 반응기 시스템의 반응 챔버일 수 있거나 이를 포함할 수 있다. 반응 챔버는 독립형 반응 챔버 또는 클러스터 툴의 일부일 수 있다.
단계(102)는, 반응 챔버 내에서 기판을 원하는 증착 온도로 가열하는 단계를 포함할 수 있다. 본 개시의 일부 구현예에서, 단계(102)는 800℃ 미만의 온도로 기판을 가열하는 단계를 포함한다. 예를 들어, 본 개시의 일부 구현예에서, 기판을 증착 온도로 가열하는 단계는 대략 20℃ 내지 대략 800℃, 650℃ 미만, 600℃ 미만, 550℃ 미만, 500℃ 미만, 약 300℃ 내지 600℃, 약 300℃ 내지 약 650℃, 약 300℃ 내지 550℃, 약 300℃ 내지 500℃, 또는 약 300℃ 내지 450℃의 온도로 기판을 가열하는 단계를 포함할 수 있다. 일부 경우에, 단계(102) 및/또는 단계(104) 동안 기판의 온도는 단계(106) 동안 기판의 온도보다 작다.
기판 온도의 제어 이외에, 반응 챔버 내의 압력도 또한 조절될 수 있다. 예를 들어, 본 개시의 일부 구현예에서, 단계(102) 및/또는 단계(104) 동안 반응 챔버 내의 압력은 760토르 미만, 또는 약 0.2 내지 약 300토르, 약 0.5 내지 약 50토르, 또는 약 0.5토르 내지 약 20토르일 수 있다. 단계(102) 및/또는 단계(104) 동안 반응 챔버 내의 압력은 몰리브덴층을 형성하는 단계 동안 압력보다 작을 수 있다. 단계(102)의 온도 및 압력은 단계(104)에 적절한 온도 및 압력이다.
단계(104)에서, 전이 금속 황화물, 전이 금속 탄화물, 및 전이 금속 질화물 중 하나 이상을 포함하는 하부층이 기판의 표면 상에 형성된다. 하부층은 주기적 CVD, ALD, 또는 하이브리드 주기적 CVD/ALD 공정과 같은 주기적 증착 공정을 사용하여 형성될 수 있다. 예를 들어, 일부 구현예에서, 특정 ALD 공정의 성장 속도는 CVD 공정에 비해 낮을 수 있다. 성장 속도를 증가시키는 하나의 접근법은 ALD 공정에서 통상적으로 사용되는 것보다 높은 증착 온도에서 작동시켜, 일부 부분에 화학 기상 증착 공정을 유발할 수 있으나, 반응물의 순차적 도입의 장점을 여전히 가질 수 있다. 이러한 공정은 주기적 CVD로 지칭될 수 있다. 일부 구현예에서, 주기적 CVD 공정은 두 개 이상의 반응물을 반응 챔버에 도입하는 단계를 포함할 수 있으며, 반응 챔버 내 두 개 이상의 반응물 사이의 중첩 시간일 수 있어서 증착의 ALD 성분 및 증착의 CVD 성분 양쪽을 초래한다. 이를 하이브리드 공정으로 지칭한다. 추가 예시에 따라, 주기적 증착 공정은 하나의 반응물/전구체의 연속적인 흐름 및 제2 반응물의 반응 챔버 내로의 주기적 펄스화를 포함할 수 있다.
본 개시의 일부 예시에 따라, 주기적 증착 공정은 열 증착 공정이다. 이들 경우, 주기적 증착 공정은, 주기적 증착 공정에 사용하기 위해 활성화된 종을 형성하는 플라즈마의 사용을 포함하지 않는다. 예를 들어, 주기적 증착 공정은 질소, 황, 또는 탄소 플라즈마의 형성 또는 사용을 포함하지 않을 수 있고, 여기된 질소, 황, 또는 탄소 종의 형성 또는 사용을 포함하지 않을 수 있고/있거나 질소, 황, 또는 탄소 라디칼의 형성 또는 사용을 포함하지 않을 수 있다.
다른 경우에, 단계(104)는 하나 이상의 전구체, 반응물 및 불활성 가스로부터 여기된 종을 형성하는 단계를 포함할 수 있다. 여기된 종은 직접식 및/또는 원격식 플라즈마를 사용하여 형성될 수 있다.
주기적 증착 공정은, 전이 금속 전구체를 반응 챔버에 제공하는 단계 및 반응물을 반응 챔버에 제공하는 단계를 (예를 들어, 별도로 및 순차적으로) 포함할 수 있다.
단계(104)에 적합한 예시적인 주기적 증착 공정(200)이 도 2에 도시되어 있다. 공정(200)은 전이 금속 전구체를 반응 챔버에 제공하는 단계(단계 202), 탄소 반응물, 황 반응물, 및 질소 반응물 중 하나 이상을 반응 챔버에 제공하는 단계(단계 204), 및 환원 반응물을 반응 챔버에 제공하는 단계(단계 206)를 포함한다. 달리 언급되지 않는 한, 단계 202-206는 도시된 순서로 수행될 필요는 없다. 예를 들어, 공정(200)은 단계(202)에 이어 단계(206)에 이어 단계(204)를 포함할 수 있다. 대안적으로, 공정(200)은 단계(202 및 204) 또는 단계(202 및 206)만을 포함할 수 있다.
전이 금속 전구체 내의 전이 금속은 4족 내지 7족 전이 금속으로부터 선택된 금속을 포함할 수 있다. 예로서, 전이 금속은 티타늄, 텅스텐, 몰리브덴, 바나듐, 니오븀, 탄탈륨, 코발트, 하프늄, 및 지르코늄으로 이루어진 군으로부터 선택될 수 있다.
본 개시의 추가적인 예에 따르면, 전이 금속 전구체는 전이 금속 할라이드, 전이 금속 칼코게나이드 할라이드, 전이 금속 카르보닐, 전이 금속유기 전구체, 및 전이 금속 유기금속 전구체 중 하나 이상을 포함할 수 있다.
예로서, 전이 금속은 몰리브덴일 수 있거나 이를 포함할 수 있다. 이 경우, 전이 금속 전구체는 몰리브덴 할라이드, 몰리브덴 옥시할라이드, 몰리브덴 유기금속 화합물, 몰리브덴 금속 유기 화합물 등 중 하나 이상을 포함할 수 있다.
특정 예로서, 몰리브덴 할라이드는 몰리브덴 플루오라이드, 몰리브덴 클로라이드, 몰리브덴 브로마이드, 및 몰리브덴 요오드 중 하나 이상으로부터 선택될 수 있다. 몰리브덴 할라이드는 몰리브덴 및 하나 이상의 할로겐만을 포함할 수 있다. 예시적인 적합한 몰리브덴 할라이드는 몰리브덴 트리클로라이드(MoCl3), 몰리브덴 테트라클로라이드(MoCl4), 몰리브덴 펜타클로라이드(MoCl5), 몰리브덴 헥사클로라이드(MoCl6), 및 몰리브덴 헥사플루오라이드(MoF6) 중 적어도 하나를 포함한다.
몰리브덴 옥시할라이드는 하나 이상의 몰리브덴 옥시할라이드, 예컨대 몰리브덴 옥시플루오라이드, 몰리브덴 옥시클로라이드, 몰리브덴 옥시브로마이드, 및 몰리브덴 옥시요오드 중 하나 이상으로부터 선택될 수 있다. 몰리브덴 옥시할라이드는 몰리브덴, 산소, 및 하나 이상의 할로겐만을 포함할 수 있다. 예로서, 몰리브덴 옥시할라이드는 브롬, 염소 및 요오드 중 하나 이상을 포함하는 화합물로부터 선택될 수 있고, 몰리브덴(V) 트리클로라이드 옥사이드(MoOCl3), 몰리브덴(VI) 테트라클로라이드 옥사이드(MoOCl4), 및 몰리브덴(IV) 디클로라이드 디옥사이드(MoO2Cl2) 중 하나 이상을 포함할 수 있다.
추가적인 예시적인 몰리브덴 전구체에는 몰리브덴 헥사카르보닐(Mo(CO)6), 테트라클로로(시클로펜타디에닐)몰리브덴, Mo(tBuN)2(NMe2)2, Mo(NBu)2(StBu)2, (Me2N)4Mo, (iPrCp)2MoH2, Mo(NMe2)4, Mo(NEt2)4, Mo2(NMe2)6, Mo(tBuN)2(NMe2)2, Mo(NtBu)2(StBu)2, Mo(NtBu)2(iPr2AMD)2, Mo(thd)3, MoO2(acac)2, MoO2(thd)2, MoO2(iPr2AMD)2, Mo(Cp)2H2, Mo(iPrCp)2H2, Mo(η6-에틸벤젠)2, MoCp(CO)2(η3-알릴), 및 MoCp(CO)2(NO)를 포함한다.
예시적인 전이 금속 전구체는 "헤테로렙틱" 또는 혼합된 리간드 전구체를 포함할 수 있으며, 여기서 임의의 달성 가능한 수(전형적으로 3 내지 5개의 리간드이지만, 예외가 있을 수 있음)의 예시적인 리간드 유형의 임의의 조합이 전이 금속/몰리브덴 원자에 부착될 수 있다. 일부 경우에, 전이 금속/몰리브덴 전구체는 적어도 하나의 할라이드 리간드를 포함한다.
할라이드 및 옥시할라이드 전구체 또는 적어도 하나의 할라이드 리간드를 포함하는 전구체의 사용은, 금속유기 전구체와 같은 다른 전구체를 사용하는 방법에 비해 유리할 수 있는데, 그 이유는 이러한 전구체, 및 특히 할라이드 및 옥시할라이드 전구체가 비교적 저렴할 수 있고, 탄소와 같은 불순물의 더 낮은 농도를 갖는 몰리브덴층을 초래할 수 있고/있거나 이러한 전구체를 사용하는 공정은 금속유기 또는 다른 몰리브덴 또는 다른 전이 금속 전구체를 사용하는 공정과 비교하여 더 제어 가능할 수 있기 때문이다. 또한, 이러한 전구체는 여기된 종을 형성하기 위해 플라즈마의 도움으로 또는 플라즈마의 도움 없이 사용될 수 있다. 또한, 유기금속 전이 금속 전구체를 사용하는 공정에 비해, 전이 금속 할라이드 전구체를 사용하는 공정은 스케일 업이 더 용이할 수 있다.
단계(204) 동안, 탄소 반응물, 황 반응물, 및 질소 반응물 중 하나 이상은 상기 반응 챔버에 제공된다.
예시적인 질소 반응물은 질소(N2), 암모니아(NH3), 히드라진(N2H4) 또는 히드라진 유도체, 수소와 질소의 혼합물, 질소 이온, 질소 라디칼, 및 여기된 질소 종, 및 다른 질소와 수소 함유 가스 중 하나 이상으로부터 선택될 수 있다. 질소 반응물은 질소 및 수소를 포함하거나 이로 구성될 수 있다. 일부 경우에, 질소 반응물은 이원자 질소를 포함하지 않는다.
예시적인 황 반응물은 황화수소(H2S), 황(예, S8), 티올(예, 알킬 및 아릴 티올), 이황화 결합을 포함한 화합물, 황-알킬기 결합을 포함한 화합물, 및 식 R-S-S-R' 또는 S-R로 표시된 화합물(여기서 R 및 R'는 지방족(예, C1-C8) 및 방향족 기, 황 할라이드(예, SCl2 또는 SBr2와 같이 하나의 황을 포함하거나 이염화이황과 같이 하나의 할라이드를 포함)을 포함한다. 알킬 티올은 C1-C8 알킬 티올을 포함할 수 있다.
예시적인 탄소 반응물은 아세틸렌, 에틸렌, 알킬 할라이드 화합물, 알켄 할라이드 화합물, 금속 알킬 화합물 등을 포함한다. 예시적인 알킬 할라이드 화합물은 CX4, CHX3, CH2X2, CH3X(X = F, Cl, Br, 또는 I)를 포함한다. 예시적인 알켄 할라이드 화합물은 C2H3X, C2H2X2, C2HX3, 및 C2X4(X = F, Cl, Br, 또는 I)를 포함한다. 예시적인 알킨 할라이드 화합물은 C2X2 및 HC2X(X = F, Cl, Br, 또는 I)를 포함한다. 예시적인 금속 알킬 화합물은 AlMe3, AlEt3, Al(iPr)3, Al(iBu)3, Al(tBu)3, GaMe3, GaEt3, Ga(iPr)3, Ga(iBu)3, Ga(tBu)3, InMe3, InEt3, In(iPr)3, In(iBu)3, In(tBu)3, 및 ZnMe2, ZnEt2을 포함한다.
단계(206)에서, 환원 반응물을 반응 챔버에 제공된다. 환원 반응물은 수소, 수소 라디칼, 수소 이온, 식 SinH(2n+2)를 갖는 실란, 식 GenH2n+2를 갖는 저메인(germane), 식 BnHn+4 또는 BnHn+6을 갖는 보란(borane), 기타 붕소 수소화물, 휘발성 금속 수소화물 및 DIBAL 및 R3N-AlH3과 같은, 이의 부가물을 포함할 수 있으며, 여기서 R은 금속과 킬레이트를 형성할 수 있는 헤테로원자를 소유하는 임의의 알킬 또는 아릴 기이다.
일부 경우에, 둘 이상의 전구체 및/또는 둘 이상의 반응물이 반응 챔버 내에서 중첩하도록, 둘 이상의 전구체 및/또는 둘 이상의 반응물이 반응 챔버로 흐를 수 있다. 예를 들어, 하나 이상의 질소 반응물 및 하나 이상의 탄소 반응물은 반응 챔버로 공동으로 흐를 수 있다.
열 주기적 증착 공정의 경우에, 반응물을 반응 챔버에 제공하는 단계의 지속 시간은, 반응물이 전구체 또는 이의 유도체와 반응할 수 있도록 비교적 길 수 있다. 예를 들어, 지속 시간은 약 0.1 내지 약 30초, 약 1 내지 약 5초, 또는 약 1.5 내지 약 10초일 수 있다.
단계(104)/공정(200)의 일부로서, 진공 및/또는 불활성 가스를 사용해 반응 챔버를 퍼지할 수 있어, 예를 들어 전구체/반응물 사이의 기상 반응을 완화시키고, 예컨대 ALD의 경우 자기 포화적 표면 반응을 가능하게 한다. 추가적으로 또는 대안적으로, 기판을, 제1 기상 반응물 및 제2 기상 반응물과 별도로 접촉하도록 이동시킬 수 있다. 반응 챔버는 전구체를 반응 챔버에 제공하는 단계 후 및/또는 반응물을 반응 챔버에 제공하는 단계 후 및/또는 환원 반응물을 반응 챔버에 제공하는 단계 후 퍼지될 수 있고 및/또는 기판은 이동된다.
본 개시의 일부 구현예에서, 공정(200)은, 단계 (1) 및/또는 단계 (2) 및/또는 단계 (3) 이후의 선택적 퍼지 또는 이동 단계와 함께, (1) 전이 금속 전구체를 반응 챔버에 제공하는 단계 및 (2) 반응물을 반응 챔버에 제공하는 단계, 및 (3) 환원 반응물을 반응 챔버에 제공하는 단계를 포함하는 유닛 증착 사이클을 반복하는 단계를 포함한다. 증착 사이클은, 예를 들어, 하부층의 원하는 두께, 예를 들어, 0nm 초과 및 10nm 미만, 약 1-10nm, 약 1-5nm, 또는 5nm 초과 및 10nm 미만에 기초하여 1회 이상 반복될 수 있다.
일단 하부층이 원하는 두께로 증착되었으면, 방법(100)은 단계(106)로 진행한다. 단계(104)와 유사하게, 단계(106)은 주기적 공정을 포함할 수 있다. 단계(106)에 적합한 예시적인 주기적 공정이 공정(300)으로서 도 3에 도시되어 있다.
공정(300)은 몰리브덴 전구체를 반응 챔버에 제공하는 단계(단계 302) 및 환원 반응물을 반응 챔버에 제공하는 단계(단계 304)를 포함한다.
단계(302) 동안, 몰리브덴 전구체가 반응 챔버, 예를 들어 단계(104)에 사용된 것과 동일한 반응 챔버에 제공된다. 몰리브덴 전구체는 전술한 임의의 몰리브덴 전구체이거나 이를 포함할 수 있다.
위에서 언급한 바와 같이, 위에서 형성된 바와 같은 하부층의 사용은 공정(300) 동안 비교적 낮은 증착 온도를 허용할 수 있다. 예를 들어, 단계(106)/공정(300) 동안의 증착 온도는 650℃ 미만, 600℃ 미만, 550℃ 미만, 500℃ 미만, 약 300℃ 내지 600℃, 약 300℃ 내지 650℃, 약 300℃ 내지 550℃, 약 300℃ 내지 500℃, 또는 약 300℃ 내지 450℃일 수 있다. 단계(106)/공정(300) 동안 반응 챔버 내의 압력은 약 0.2 내지 약 300토르, 약 0.5 내지 약 60토르, 또는 약 20 내지 약 80토르일 수 있다. 전술한 바와 같이, 단계(106) 동안 기판 온도 및/또는 반응 챔버 압력은 단계(102) 및/또는 단계(104) 동안 기판 온도 및/또는 반응 챔버 압력보다 높을 수 있다.
본 개시의 다양한 예에 따라, 온도, 압력, 전구체 유량, 반응물 유량, 및 여기 종의 형성 여부와 같은 공정 조건이 단계(104 및/또는 106) 동안 하나 이상의 공정 조건을 조작함으로써 몰리브덴 층의 응력을 조작하는 데 사용될 수 있다. 예를 들어, 하부층의 사용은 낮은 온도에서 몰리브덴층의 증착을 허용한다. 단계(104)(하부층의 형성) 동안의 공정 조건은 위에 놓이는 몰리브덴층의 응력을 조작하도록 조작될 수 있다. 전술한 온도와 같은 더 낮은 온도에서 (예를 들어, 알루미늄 옥사이드와 같은 유전체 재료 위로) 증착된 몰리브덴층은 하부층 없이 및/또는 더 높은 온도에서 증착된 몰리브덴층에 비해 상대적으로 더 큰 압축 응력을 갖는 몰리브덴층을 허용한다. 또한, 단계(104 및 106) 동안 공정 조건을 제어함으로써, 몰리브덴층에 응력 변조를 갖고, 예를 들어 20nm 몰리브덴층에 대해 최대 약 450MPa 또는 200MPa 초과의 층에 압축 응력을 달성할 수 있다.
구체적인 실시예
이하에 제공된 구체적인 실시예들은 단지 예시일 뿐이며 예시를 위해 제시된다. 달리 언급되지 않는 한, 범위는 본 개시의 범주를 한정하고자 하는 것은 아니다.
도 6 내지 도 8은 다양한 조건을 사용하여 알루미늄 산화물층 위에 놓여 형성된 몰리브덴층의 막 응력을 도시하며, 공정 조건 및/또는 본 개시에 따른 하부층의 특성이 위에 놓이는 몰리브덴층의 응력을 조작하는 데 어떻게 사용될 수 있는지에 대한 실시예를 도시하고 있다. 도 6은 하부층(602) 없이; 2토르 및 450℃에서, 0.25 s 몰리브덴 전구체(예를 들어, MoO2Cl2) 펄스, 20 s 질소 펄스(예를 들어, NH3), 6 s 환원제(예를 들어, H2) 펄스를 사용하여 형성된 몰리브덴층을 가지고 (604) (전처리1); 8토르 및 500℃에서, 0.25 s 몰리브덴 전구체 펄스, 60 s 환원제 펄스, 및 0.1 s 질소 반응물 펄스를 사용하여 형성된 몰리브덴층을 가지고 (606) (전처리2); 및 2토르 및 450℃에서, 1 s 몰리브덴 전구체, 30 s 질소 반응물, 5 s 환원제 (608) (전처리3), 증착된 몰리브덴층에 대한 응력 값을 도시한다. 하부층 두께는 약 20Å이었다. 몰리브덴층 증착 단계 동안의 온도는 약 550℃였다.
도 7은 다양한 하부층 두께를 갖는 기판 위에 증착된 몰리브덴층의 응력을 도시한다. 특히, 하부층(702) 없이, 약 10Å 하부층(704), 약 20Å 하부층(706), 및 약 30Å 하부층(708)을 가지고, 알루미늄 산화물층 위에 형성된 몰리브덴 막에 대한 응력 값이 도시되어 있다. 도 7의 층을 형성하기 위한 조건은, 변화된 사이클 수를 제외하고는, 전처리1의 조건과 유사하였다.
도 8은 몰리브덴층 증착 동안 온도의 효과를 도시한다. 특히, 하부층(802) 없이, 약 550℃에서 형성된 몰리브덴(804)을 가지고, 약 525℃에서 형성된 몰리브덴(806)을 가지고, 및 약 475℃에서 형성된 몰리브덴(808)을 가지고, 알루미늄 산화물층 위에 형성된 몰리브덴 막에 대한 응력 값이 도시되어 있다. 도 8에 도시된 응력 값으로 층을 형성하는 조건은 전처리1의 조건과 유사하였다.
일부 구현예에서, 몰리브덴층의 스텝 커버리지는, 약 2 초과, 약 5 초과, 약 10 초과, 약 25 초과, 약 50 초과, 약 100 초과, 또는 약 10 내지 100 또는 약 5 내지 약 25의 종횡비(높이/폭)를 갖는 구조체 내/구조체 상에서, 약 50% 이상, 또는 약 80% 이상, 또는 약 90% 이상, 또는 약 95%, 또는 약 98%, 또는 약 99% 이상이다.
도 4는 본 개시의 추가적인 예시에 따른 장치(400)의 구조체/일부를 나타낸다. 장치부 또는 구조체(400)는 기판(402), 몰리브덴층(404), 및 (예를 들어, 하나 또는 둘 모두와 접촉하는) 기판(402)과 몰리브덴층(404) 사이의 하부층(406)을 포함한다.
기판(402)은 본원에 설명된 임의의 기판 재료일 수 있거나 이를 포함할 수 있다. 본 개시의 예에 따르면, 기판(402)은 유전체 또는 절연층을 포함한다.
유전체 또는 절연층은 하나 이상의 유전체 또는 절연 재료 층을 포함할 수 있다. 예로서, 고 유전체 또는 절연 층은, 예를 들어 약 7 초과의 유전 상수를 갖는 금속성 옥사이드와 같은 고-유전율 재료일 수 있다. 일부 구현예에서, 고-유전율 재료는 실리콘 옥사이드의 유전 상수보다 높은 유전 상수를 포함한다. 예시적인 고-유전율 재료는 하프늄 옥사이드(HfO2), 탄탈륨 옥사이드(Ta2O5), 지르코늄 옥사이드(ZrO2), 티타늄 옥사이드(TiO2), 하프늄 실리케이트(HfSiOx), 알루미늄 옥사이드(Al2O3), 란타늄 옥사이드(La2O3), 티타늄 니트라이드 및 하나 이상의 이러한 층을 포함한 혼합물/라미네이트를 포함한다.
몰리브덴층(404) 및 하부층(406)은 본원에 기술된 방법에 따라 형성될 수 있다. 하부층(406)이 주기적 증착 공정을 사용하여 형성되는 경우에, 하부층(406)의 하단에서 하부층(406)의 상단까지, 예를 들어 하나 이상의 증착 사이클 동안 전구체 및/또는 반응물(들)의 양 및/또는 각각의 펄스 시간을 제어함으로써, 하부층(406) 성분(예를 들어, 전이 금속, C, S, 또는 N)의 농도가 달라질 수 있다. 일부 경우에, 몰리브덴층(404)은 몰리브덴 금속일 수 있다. 몰리브덴층(404)의 응력은, 하부층(406)의 형성 동안 특성(예를 들어, 두께 및/또는 조성물) 및/또는 공정 조건을 변경함으로써 변경될 수 있다.
몰리브덴층(404)은 1원자% 미만, 0.2원자% 미만, 0.1원자% 미만, 또는 0.05원자% 미만을, 단독으로 또는 조합하여, 할라이드, 수소 등과 같은 불순물을 포함할 수 있다.
추가적으로 또는 대안적으로, 몰리브덴층(404)은, 예를 들어 방법(100)을 사용하여, < 5nm, < 4nm, < 3nm, < 2nm, < 1.5nm, < 1.2nm, < 1.0nm, 또는 < 0.9nm의 두께로 연속적인 막을 형성할 수 있다.
도 5는, 본 개시의 예시적인 추가 구현예에 따른 시스템(500)을 나타낸다. 시스템(500)은, 본원에 설명된 바와 같은 방법 또는 공정을 수행하고/수행하거나 본원에 설명된 바와 같은 구조체 또는 장치를 형성하기 위해 사용될 수 있다.
도시된 예에서, 시스템(500)은 하나 이상의 반응 챔버(502), 전구체 가스 공급원(504), 반응물 가스 공급원(506), 환원 반응물 공급원(507), 퍼지 가스 공급원(508), 배기 공급원(510), 및 제어기(512)를 포함한다.
반응 챔버(502)는 임의의 적합한 반응 챔버, 예컨대 ALD 또는 CVD 반응 챔버를 포함할 수 있다.
전구체 가스 공급원(504)은, 용기 및 본원에 설명된 바와 같은 하나 이상의 몰리브덴 전구체를 단독으로 또는 하나 이상의 캐리어(예를 들어, 불활성) 가스와 혼합하여 포함할 수 있다. 반응물 가스 공급원(506)은, 용기 및 본원에 설명된 바와 같은 하나 이상의 반응물을 단독으로 또는 하나 이상의 캐리어 가스와 혼합하여 포함할 수 있다. 환원 반응물 공급원(507)은 하나 이상의 환원 반응물을 단독으로 또는 하나 이상의 캐리어 가스와 혼합하여 포함할 수 있다. 퍼지 가스 공급원(508)은 본원에 설명된 바와 같이 하나 이상의 불활성 가스를 포함할 수 있다. 네 개의 가스 공급원들(504, 506, 507 및 508)으로 나타냈지만, 시스템(500)은 적절한 임의 개수의 가스 공급원을 포함할 수 있다. 예를 들어, 시스템(500)은 다른 전이 금속 전구체 공급원 및/또는 다른 환원 반응물을 포함할 수 있다. 가스 공급원들(504, 506, 507 및 508)은 라인들(514, 516, 518 및 519)을 통해 반응 챔버(502)에 결합될 수 있으며, 이들 각각은 흐름 제어기, 밸브, 히터 등을 포함할 수 있다.
진공원(510)은 하나 이상의 진공 펌프를 포함할 수 있다.
제어기(512)는 밸브, 매니폴드, 히터, 펌프 및 시스템(500)에 포함된 다른 구성 요소를 선택적으로 작동시키기 위한 전자 회로 및 소프트웨어를 포함한다. 이러한 회로 및 구성 요소는, 전구체, 반응물 및 퍼지 가스를 각각의 공급원들(504, 506, 507 및 508)로부터 도입하기 위해 작동한다. 제어기(512)는 가스 펄스 순서의 시점, 기판 및/또는 반응 챔버의 온도, 반응 챔버의 압력, 및 시스템(500)의 적절한 작동을 제공하는데 다양한 기타 작동을 제어할 수 있다. 제어기(512)는, 반응 챔버(502) 내로 그리고 반응 챔버로부터의 전구체, 반응물 및 퍼지 가스의 흐름을 제어하기 위한 밸브를 전기식 혹은 공압식으로 제어하는 제어 소프트웨어를 포함할 수 있다. 제어기(512)는, 소프트웨어 또는 하드웨어 구성 요소, 예를 들어 특정 작업을 수행하는 FPGA 또는 ASIC과 같은 모듈을 포함할 수 있다. 모듈은 제어 시스템의 어드레스 가능한 저장 매체에 탑재되도록 구성되고, 하나 이상의 공정을 실행하도록 유리하게 구성될 수 있다.
시스템(500)은 원격 및/또는 직접 플라즈마 생성 장치와 같은 하나 이상의 원격 여기 공급원(520) 및/또는 직접 여기 공급원(522)을 포함할 수 있다.
상이한 수 및 종류의 전구체 및 반응물 공급원 및 퍼지 가스 공급원을 포함하는 시스템(500)의 다른 구성이 가능하다. 또한, 가스를 반응 챔버(502) 내로 선택적으로 공급하는 목적을 달성하는데 사용될 수 있는 밸브, 도관, 전구체 공급원, 퍼지 가스 공급원의 다수의 배열이 존재함을 이해할 것이다. 또한, 시스템을 개략적으로 표현하면서, 많은 구성 요소가 예시의 단순화를 위해 생략되었는데, 이러한 구성 요소는, 예를 들어 다양한 밸브, 매니폴드, 정화기, 히터, 용기, 벤트, 및/또는 바이패스를 포함할 수 있다.
반응기 시스템(500)의 작동 중에, 반도체 웨이퍼(미도시)와 같은 기판은, 예를 들어 기판 취급 시스템에서 반응 챔버(502)로 이송된다. 일단 기판(들)이 반응 챔버(502)로 이송되면, 전구체, 반응물, 캐리어 가스, 및/또는 퍼지 가스와 같은, 가스 공급원들(504, 506, 507 및 508)로부터 하나 이상의 가스가 반응 챔버(502) 내로 유입된다.
전술한 본 개시의 예시적 구현예는 본 발명의 범주를 제한하지 않는데, 그 이유는 이들 구현예는 본 발명의 구현예의 예시일 뿐이기 때문이며, 이는 첨부된 청구범위 및 그의 법적 균등물에 의해 정의된다. 임의의 균등한 구현예는 본 발명의 범주 내에 있도록 의도된다. 확실하게, 본원에 나타내고 설명된 것 외에도, 설명된 요소의 대안적인 유용한 조합과 같은 본 발명의 다양한 변경은 설명으로부터 당업자에게 분명할 수 있다. 이러한 변경예 및 구현예도 첨부된 청구범위의 범주 내에 있는 것으로 의도된다.
Claims (21)
- 구조체를 형성하는 방법으로서, 상기 방법은,
기판을 제공하는 단계;
상기 기판의 표면 상에 전이금속 황화물, 전이금속 탄화물, 및 전이금속 질화물 중 하나 이상을 포함하는 하부층을 형성하는 단계; 및
상기 하부층 위에 놓이는 몰리브덴층을 형성하는 단계를 포함하는, 방법. - 제1항에 있어서, 상기 하부층은 상기 전이금속 질화물을 포함하는, 방법.
- 제1항 또는 제2항에 있어서, 상기 하부층은 4족 내지 7족 전이 금속으로부터 선택된 전이 금속을 포함하는, 방법.
- 제1항 내지 제3항 중 어느 한 항에 있어서, 상기 하부층의 두께는 0nm 초과 및 10nm 미만, 약 1-10nm, 약 1-5nm, 또는 5nm 초과 및 10nm 미만인, 방법.
- 제1항 내지 제4항 중 어느 한 항에 있어서, 상기 하부층을 형성하는 단계는 주기적 증착 공정을 포함하는, 방법.
- 제5항에 있어서, 상기 주기적 증착 공정은:
전이 금속 전구체를 반응 챔버에 제공하는 단계;
탄소, 황, 및 질소 반응물 중 하나 이상을 상기 반응 챔버에 제공하는 단계; 및
선택적으로 환원 반응물을 상기 반응 챔버에 제공하는 단계를 포함하는, 방법. - 제6항에 있어서, 상기 전이 금속 전구체는 전이 금속 할라이드, 전이 금속 칼코게나이드 할라이드, 전이 금속 카르보닐, 전이 금속유기 전구체, 및 전이 금속 유기금속 전구체 중 하나 이상을 포함하는, 방법.
- 제6항 또는 제7항에 있어서, 상기 탄소 반응물은 아세틸렌, 에틸렌, 알킬 할라이드 화합물, 알켄 할라이드 화합물, 및 금속 알킬 화합물 중 하나 이상을 포함하는, 방법.
- 제6항 내지 제8항 중 어느 한 항에 있어서, 상기 질소 반응물은 질소(N2), 암모니아(NH3), 히드라진(N2H4) 또는 히드라진 유도체, 수소와 질소의 혼합물, 질소 이온들, 질소 라디칼들, 및 여기된 질소 종 중 하나 이상을 포함하는, 방법.
- 제6항 내지 제9항 중 어느 한 항에 있어서, 상기 황 반응물은 황화수소(H2S), 황, 티올, 이황화 결합을 포함하는 화합물, 황-알킬기 결합을 포함하는 화합물, 및 식 R-S-S-R' 또는 S-R로 표시되는 화합물 중 하나 이상을 포함하고, 여기서 R 및 R'는 지방족 및 방향족 기들과 황 할라이드들로부터 독립적으로 선택되는, 방법.
- 제6항 내지 제10항 중 어느 한 항에 있어서, 상기 환원 반응물은 수소, 수소 라디칼들, 수소 이온들, 식 SinH(2n+2)를 갖는 실란, 식 GenH2n+2를 갖는 저메인, 및 식 BnHn+4 또는 BnHn+6을 갖는 보란 중 하나 이상을 포함하는, 방법.
- 제1항 내지 제11항 중 어느 한 항에 있어서, 상기 몰리브덴층을 형성하는 단계는 주기적 증착 공정을 포함하는, 방법.
- 제12항에 있어서, 상기 주기적 증착 공정은:
몰리브덴 전구체를 반응 챔버에 제공하는 단계; 및
환원 반응물을 상기 반응 챔버에 제공하는 단계를 포함하는, 방법. - 제13항에 있어서, 상기 몰리브덴 전구체는 몰리브덴 할라이드, 몰리브덴 칼코게나이드 할라이드, 몰리브덴 카르보닐, 몰리브덴 금속유기 전구체, 및 몰리브덴 유기금속 전구체 중 하나 이상을 포함하는, 방법.
- 제13항 또는 제14항에 있어서, 상기 몰리브덴 전구체는 적어도 하나의 할라이드 리간드를 포함하는 방법.
- 제13항 내지 제15항 중 어느 한 항에 있어서, 상기 몰리브덴 전구체는 몰리브덴 트리클로라이드(MoCl3), 몰리브덴 테트라클로라이드(MoCl4), 몰리브덴 펜타클로라이드(MoCl5), 몰리브덴 헥사클로라이드(MoCl6), 몰리브덴 헥사플루오라이드(MoF6), 몰리브덴 헥사카르보닐(Mo(CO)6), 테트라클로로(시클로펜타디에닐)몰리브덴, 몰리브덴(V) 트리클로라이드 옥사이드(MoOCl3), 몰리브덴(VI) 테트라클로라이드 옥사이드(MoOCl4), 및 몰리브덴(IV) 디클로라이드 디옥사이드(MoO2Cl2), Mo(tBuN)2(NMe2)2, Mo(NBu)2(StBu)2, (Me2N)4Mo, (iPrCp)2MoH2, Mo(NMe2)4, Mo(NEt2)4, Mo2(NMe2)6, Mo(tBuN)2(NMe2)2, Mo(NtBu)2(StBu)2, Mo(NtBu)2(iPr2AMD)2, Mo(thd)3, MoO2(acac)2, MoO2(thd)2, MoO2(iPr2AMD)2, Mo(Cp)2H2, Mo(iPrCp)2H2, Mo(η6-에틸벤젠)2, MoCp(CO)2(η3-알릴), 및 MoCp(CO)2(NO) 중 하나 이상을 포함하는, 방법.
- 제13항 내지 제16항 중 어느 한 항에 있어서, 상기 몰리브덴층을 형성하는 단계 동안 증착 온도는 650℃ 미만, 600℃ 미만, 550℃ 미만, 500℃ 미만, 약 300℃ 내지 650℃, 약 300℃ 내지 600℃, 약 300℃ 내지 550℃, 약 300℃ 내지 500℃, 또는 약 300℃ 내지 450℃인, 방법.
- 제1항 내지 제17항 중 어느 한 항에 있어서, 상기 하부층은 상기 몰리브덴층 내의 응력을 조작하는 데 사용되는, 방법.
- 제1항 내지 제18항 중 어느 한 항에 있어서, 상기 하부층은 배리어 층인, 방법.
- 제1항 내지 제19항 중 어느 한 항의 방법에 따라 형성된 구조체.
- 제1항 내지 제19항 중 어느 한 항의 방법을 수행하는 반응기 시스템.
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2021
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- 2021-07-14 KR KR1020210092540A patent/KR20220011093A/ko unknown
- 2021-07-15 US US17/376,238 patent/US11674220B2/en active Active
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- 2021-07-16 CN CN202110804662.4A patent/CN113957410A/zh active Pending
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2023
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Cited By (1)
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KR102558286B1 (ko) * | 2022-07-21 | 2023-07-25 | 주식회사 엘엠케이 | 구리 연속 증착 소스 |
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US11674220B2 (en) | 2023-06-13 |
US20230279539A1 (en) | 2023-09-07 |
JP2022020584A (ja) | 2022-02-01 |
CN113957410A (zh) | 2022-01-21 |
TW202204662A (zh) | 2022-02-01 |
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