CN117015630A - Metal thin film precursor composition, thin film forming method using the same, and semiconductor substrate manufactured by the method - Google Patents
Metal thin film precursor composition, thin film forming method using the same, and semiconductor substrate manufactured by the method Download PDFInfo
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- CN117015630A CN117015630A CN202280018618.3A CN202280018618A CN117015630A CN 117015630 A CN117015630 A CN 117015630A CN 202280018618 A CN202280018618 A CN 202280018618A CN 117015630 A CN117015630 A CN 117015630A
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- Prior art keywords
- thin film
- chamber
- growth regulator
- film precursor
- substrate
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- 239000010409 thin film Substances 0.000 title claims abstract description 236
- 239000002243 precursor Substances 0.000 title claims abstract description 172
- 238000000034 method Methods 0.000 title claims abstract description 143
- 239000000758 substrate Substances 0.000 title claims abstract description 99
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 88
- 239000002184 metal Substances 0.000 title claims abstract description 88
- 239000000203 mixture Substances 0.000 title claims abstract description 68
- 239000004065 semiconductor Substances 0.000 title claims abstract description 21
- 239000003630 growth substance Substances 0.000 claims abstract description 125
- 150000001875 compounds Chemical class 0.000 claims abstract description 124
- 230000008569 process Effects 0.000 claims abstract description 69
- 239000010408 film Substances 0.000 claims description 187
- 238000010926 purge Methods 0.000 claims description 86
- 239000000460 chlorine Substances 0.000 claims description 59
- 238000000151 deposition Methods 0.000 claims description 57
- 239000000126 substance Substances 0.000 claims description 57
- 230000008021 deposition Effects 0.000 claims description 53
- 239000007789 gas Substances 0.000 claims description 52
- 238000000231 atomic layer deposition Methods 0.000 claims description 45
- 229910052799 carbon Inorganic materials 0.000 claims description 38
- 229910052731 fluorine Inorganic materials 0.000 claims description 32
- 239000012495 reaction gas Substances 0.000 claims description 31
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- 229910052801 chlorine Inorganic materials 0.000 claims description 26
- 229910052739 hydrogen Inorganic materials 0.000 claims description 26
- 229910052757 nitrogen Inorganic materials 0.000 claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 22
- 229910052740 iodine Inorganic materials 0.000 claims description 22
- 229910052794 bromium Inorganic materials 0.000 claims description 20
- 125000004432 carbon atom Chemical group C* 0.000 claims description 19
- 150000002367 halogens Chemical group 0.000 claims description 19
- 229910052760 oxygen Inorganic materials 0.000 claims description 19
- 238000005229 chemical vapour deposition Methods 0.000 claims description 18
- 239000011737 fluorine Substances 0.000 claims description 18
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 17
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 17
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims description 17
- 230000008016 vaporization Effects 0.000 claims description 17
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 15
- 229910052717 sulfur Inorganic materials 0.000 claims description 15
- 229910052698 phosphorus Inorganic materials 0.000 claims description 14
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 13
- 229910052721 tungsten Inorganic materials 0.000 claims description 13
- 239000003446 ligand Substances 0.000 claims description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 239000011593 sulfur Substances 0.000 claims description 10
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 239000011630 iodine Substances 0.000 claims description 9
- 150000004767 nitrides Chemical class 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- 150000001923 cyclic compounds Chemical class 0.000 claims description 7
- 239000007800 oxidant agent Substances 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 150000002431 hydrogen Chemical group 0.000 claims description 6
- 238000005121 nitriding Methods 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- 229910052770 Uranium Inorganic materials 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 150000001491 aromatic compounds Chemical class 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 239000006227 byproduct Substances 0.000 abstract description 36
- 230000001603 reducing effect Effects 0.000 abstract description 16
- 230000007797 corrosion Effects 0.000 abstract description 14
- 238000005260 corrosion Methods 0.000 abstract description 14
- 238000007086 side reaction Methods 0.000 abstract description 11
- 230000015556 catabolic process Effects 0.000 abstract description 5
- 238000006731 degradation reaction Methods 0.000 abstract description 5
- 238000000427 thin-film deposition Methods 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 50
- 230000008901 benefit Effects 0.000 description 41
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 32
- BQBYSLAFGRVJME-UHFFFAOYSA-L molybdenum(2+);dichloride Chemical compound Cl[Mo]Cl BQBYSLAFGRVJME-UHFFFAOYSA-L 0.000 description 27
- 239000010936 titanium Substances 0.000 description 24
- 230000001976 improved effect Effects 0.000 description 23
- 239000012535 impurity Substances 0.000 description 21
- 238000002347 injection Methods 0.000 description 21
- 239000007924 injection Substances 0.000 description 21
- 239000010410 layer Substances 0.000 description 20
- 229910052786 argon Inorganic materials 0.000 description 16
- 229910052736 halogen Inorganic materials 0.000 description 16
- -1 aluminum Chemical class 0.000 description 14
- 239000007788 liquid Substances 0.000 description 14
- 239000006200 vaporizer Substances 0.000 description 14
- 238000002474 experimental method Methods 0.000 description 13
- 238000001179 sorption measurement Methods 0.000 description 12
- 229910052719 titanium Inorganic materials 0.000 description 12
- 230000006872 improvement Effects 0.000 description 11
- 239000012808 vapor phase Substances 0.000 description 10
- 239000004215 Carbon black (E152) Substances 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- 229930195733 hydrocarbon Natural products 0.000 description 9
- 150000002430 hydrocarbons Chemical class 0.000 description 9
- 230000001965 increasing effect Effects 0.000 description 9
- 229910052750 molybdenum Inorganic materials 0.000 description 9
- 239000011733 molybdenum Substances 0.000 description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000012454 non-polar solvent Substances 0.000 description 8
- 230000009257 reactivity Effects 0.000 description 8
- ANGGPYSFTXVERY-UHFFFAOYSA-N 2-iodo-2-methylpropane Chemical compound CC(C)(C)I ANGGPYSFTXVERY-UHFFFAOYSA-N 0.000 description 7
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 7
- 230000006866 deterioration Effects 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 229910044991 metal oxide Inorganic materials 0.000 description 7
- 150000004706 metal oxides Chemical class 0.000 description 7
- 230000001629 suppression Effects 0.000 description 7
- 239000010937 tungsten Substances 0.000 description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 6
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 6
- 239000010955 niobium Chemical group 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 230000001105 regulatory effect Effects 0.000 description 6
- 238000001004 secondary ion mass spectrometry Methods 0.000 description 6
- 238000012546 transfer Methods 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- KMGBZBJJOKUPIA-UHFFFAOYSA-N butyl iodide Chemical compound CCCCI KMGBZBJJOKUPIA-UHFFFAOYSA-N 0.000 description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- 229910052758 niobium Chemical group 0.000 description 5
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical group [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 5
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229910052581 Si3N4 Inorganic materials 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- 239000003990 capacitor Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 150000001924 cycloalkanes Chemical class 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 4
- IQRUSQUYPCHEKN-UHFFFAOYSA-N 2-iodobutane Chemical compound CCC(C)I IQRUSQUYPCHEKN-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical group [Ti]#N NRTOMJZYCJJWKI-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
- 125000001246 bromo group Chemical group Br* 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000001747 exhibiting effect Effects 0.000 description 3
- 229910052732 germanium Inorganic materials 0.000 description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical group [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 3
- 229910052735 hafnium Inorganic materials 0.000 description 3
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical group [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 229910052741 iridium Inorganic materials 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- AOLPZAHRYHXPLR-UHFFFAOYSA-I pentafluoroniobium Chemical compound F[Nb](F)(F)(F)F AOLPZAHRYHXPLR-UHFFFAOYSA-I 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 description 2
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- XMYFZAWUNVHVGI-UHFFFAOYSA-N 3-ethylpent-2-ene Chemical compound CCC(CC)=CC XMYFZAWUNVHVGI-UHFFFAOYSA-N 0.000 description 2
- GAVSPGFGYWCFSO-UHFFFAOYSA-N 3-iodo-2,4-dimethylpentane Chemical compound CC(C)C(I)C(C)C GAVSPGFGYWCFSO-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 229910016062 BaRuO Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
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- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 2
- 229910019800 NbF 5 Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 229910004121 SrRuO Inorganic materials 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 150000001337 aliphatic alkines Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- GPBUGPUPKAGMDK-UHFFFAOYSA-N azanylidynemolybdenum Chemical compound [Mo]#N GPBUGPUPKAGMDK-UHFFFAOYSA-N 0.000 description 2
- CVCSGXJPONFHRC-UHFFFAOYSA-N carbon monoxide;cobalt;nitroxyl anion Chemical group [Co].[O+]#[C-].[O+]#[C-].[O+]#[C-].O=[N-] CVCSGXJPONFHRC-UHFFFAOYSA-N 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000005137 deposition process Methods 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- PDPJQWYGJJBYLF-UHFFFAOYSA-J hafnium tetrachloride Chemical compound Cl[Hf](Cl)(Cl)Cl PDPJQWYGJJBYLF-UHFFFAOYSA-J 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- FUCOMWZKWIEKRK-UHFFFAOYSA-N iodocyclohexane Chemical compound IC1CCCCC1 FUCOMWZKWIEKRK-UHFFFAOYSA-N 0.000 description 2
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- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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- RLCOZMCCEKDUPY-UHFFFAOYSA-H molybdenum hexafluoride Chemical compound F[Mo](F)(F)(F)(F)F RLCOZMCCEKDUPY-UHFFFAOYSA-H 0.000 description 2
- GICWIDZXWJGTCI-UHFFFAOYSA-I molybdenum pentachloride Chemical compound Cl[Mo](Cl)(Cl)(Cl)Cl GICWIDZXWJGTCI-UHFFFAOYSA-I 0.000 description 2
- OYMJNIHGVDEDFX-UHFFFAOYSA-J molybdenum tetrachloride Chemical compound Cl[Mo](Cl)(Cl)Cl OYMJNIHGVDEDFX-UHFFFAOYSA-J 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
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- MJLVTPJYMZVBPF-UHFFFAOYSA-N 3-bromo-2,4-dimethylpentane Chemical compound CC(C)C(Br)C(C)C MJLVTPJYMZVBPF-UHFFFAOYSA-N 0.000 description 1
- FCPXHGJZKRXGJY-UHFFFAOYSA-N 3-chloro-2-methylpentane Chemical compound CCC(Cl)C(C)C FCPXHGJZKRXGJY-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
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- 101000735417 Homo sapiens Protein PAPPAS Proteins 0.000 description 1
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 102100034919 Protein PAPPAS Human genes 0.000 description 1
- 229910003902 SiCl 4 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910002367 SrTiO Inorganic materials 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 229910006501 ZrSiO Inorganic materials 0.000 description 1
- FBRZKYHOEHMDRJ-UHFFFAOYSA-K [Cl-].[In+3].Cl.[Cl-].[Cl-] Chemical compound [Cl-].[In+3].Cl.[Cl-].[Cl-] FBRZKYHOEHMDRJ-UHFFFAOYSA-K 0.000 description 1
- 229910052768 actinide Inorganic materials 0.000 description 1
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- KXADPELPQCWDHL-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1.COC1=CC=CC=C1 KXADPELPQCWDHL-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- AQNQQHJNRPDOQV-UHFFFAOYSA-N bromocyclohexane Chemical compound BrC1CCCCC1 AQNQQHJNRPDOQV-UHFFFAOYSA-N 0.000 description 1
- BRTFVKHPEHKBQF-UHFFFAOYSA-N bromocyclopentane Chemical compound BrC1CCCC1 BRTFVKHPEHKBQF-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- UHZZMRAGKVHANO-UHFFFAOYSA-M chlormequat chloride Chemical compound [Cl-].C[N+](C)(C)CCCl UHZZMRAGKVHANO-UHFFFAOYSA-M 0.000 description 1
- NDTCXABJQNJPCF-UHFFFAOYSA-N chlorocyclopentane Chemical compound ClC1CCCC1 NDTCXABJQNJPCF-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- MQIKJSYMMJWAMP-UHFFFAOYSA-N dicobalt octacarbonyl Chemical group [Co+2].[Co+2].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] MQIKJSYMMJWAMP-UHFFFAOYSA-N 0.000 description 1
- NZZFYRREKKOMAT-UHFFFAOYSA-N diiodomethane Chemical compound ICI NZZFYRREKKOMAT-UHFFFAOYSA-N 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- FEEFWFYISQGDKK-UHFFFAOYSA-J hafnium(4+);tetrabromide Chemical compound Br[Hf](Br)(Br)Br FEEFWFYISQGDKK-UHFFFAOYSA-J 0.000 description 1
- 150000004820 halides Chemical group 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000001475 halogen functional group Chemical group 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
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical group [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- PCEBAZIVZVIQEO-UHFFFAOYSA-N iodocyclopentane Chemical compound IC1CCCC1 PCEBAZIVZVIQEO-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- QRXWMOHMRWLFEY-UHFFFAOYSA-N isoniazide Chemical compound NNC(=O)C1=CC=NC=C1 QRXWMOHMRWLFEY-UHFFFAOYSA-N 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- JUHDUIDUEUEQND-UHFFFAOYSA-N methylium Chemical group [CH3+] JUHDUIDUEUEQND-UHFFFAOYSA-N 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- UNFUYWDGSFDHCW-UHFFFAOYSA-N monochlorocyclohexane Chemical compound ClC1CCCCC1 UNFUYWDGSFDHCW-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 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
- 238000012360 testing method Methods 0.000 description 1
- WWJBJTBTXOHQAZ-UHFFFAOYSA-J tetrabromomolybdenum Chemical compound Br[Mo](Br)(Br)Br WWJBJTBTXOHQAZ-UHFFFAOYSA-J 0.000 description 1
- YXPHMGGSLJFAPL-UHFFFAOYSA-J tetrabromotungsten Chemical compound Br[W](Br)(Br)Br YXPHMGGSLJFAPL-UHFFFAOYSA-J 0.000 description 1
- 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 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- ZVWKZXLXHLZXLS-UHFFFAOYSA-N zirconium nitride Chemical compound [Zr]#N ZVWKZXLXHLZXLS-UHFFFAOYSA-N 0.000 description 1
- LSWWNKUULMMMIL-UHFFFAOYSA-J zirconium(iv) bromide Chemical compound Br[Zr](Br)(Br)Br LSWWNKUULMMMIL-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/06—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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
- C23C16/45534—Use of auxiliary reactants other than used for contributing to the composition of the main film, e.g. catalysts, activators or scavengers
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45553—Atomic layer deposition [ALD] characterized by the use of precursors specially adapted for ALD
Abstract
The present invention relates to a metal thin film precursor composition, a thin film forming method using the same, and a semiconductor substrate manufactured by the method, and provides a metal thin film precursor composition comprising a metal thin film precursor compound and a growth regulator having a predetermined end group and structure, which is used in a thin film deposition process to suppress side reactions, and to appropriately control a thin film growth rate and remove process byproducts in the thin film, thereby greatly improving step coverage (step coverage), thickness uniformity of the thin film, and resistivity characteristics, reducing corrosion and degradation, improving crystallinity of the thin film, and thus improving electrical characteristics of the thin film, even if the thin film is deposited on a substrate having a complicated structure.
Description
Technical Field
The present invention relates to a metal thin film precursor composition, a thin film forming method using the same, and a semiconductor substrate manufactured by the method, and more particularly, to a metal thin film precursor composition which suppresses side reactions to reduce impurity concentration in a thin film and prevent corrosion and degradation of the thin film to improve electrical characteristics of the thin film, and also appropriately controls a growth rate of the thin film, thereby improving step coverage (step coverage), thickness uniformity of the thin film, and resistivity even if the thin film is formed on a substrate having a complicated structure, and which does not decompose even when used in combination with a thin film precursor, a thin film forming method using the same, and a semiconductor substrate manufactured by the method.
Background
The integration of memory and non-memory semiconductor devices is increasing day by day, and as the structure thereof is becoming more and more complex, the importance of the film quality and step coverage (stepcoverage) of thin films is also increasing when depositing various thin films onto a substrate.
The thin film for semiconductor is formed of a metal nitride, silicon nitride, metal oxide, silicon oxide, a metal thin film, or the like. As the metal nitride film or the silicon nitride film, there is titanium nitride (TiN), tantalum nitride (TaN), zirconium nitride (ZrN), alN, tiSiN, tiAlN, tiBN, tiON, tiCN, siN, or the like, and the film is generally used as a silicon layer of an impurity semiconductor and an anti-diffusion film (diffusion barrier) of aluminum (Al), copper (Cu), or the like used as an interlayer wiring material. Among them, tungsten (W), molybdenum (Mo) metal thin films, and the like are used as an adhesion layer (adhesion layer) when depositing a substrate. As the metal oxide film or silicon oxide film, there is developed a film comprising SiO 2 、ZrO 2 、HfO 2 、TiO 2 The metal thin film includes Ti, mo, W, co of various kindsEtc., the films are typically used for dielectric, insulation, wiring, etc.
In order for a thin film deposited on a substrate to have excellent and uniform physical properties, the formed thin film must have high step coverage. Thus, atomic layer deposition (atomic layer deposition; ALD) processes utilizing surface reactions are more employed than chemical vapor deposition (chemical vapor deposition; CVD) processes utilizing primarily vapor phase reactions, but there are still problems in achieving 100% step coverage.
Further, as a method for improving step coverage, a method of reducing the growth rate of a thin film is proposed, but when the deposition temperature is reduced in order to reduce the growth rate of a thin film, the residual amount of impurities such as carbon and chlorine in the thin film is increased, thereby greatly reducing the film quality.
In addition, when titanium tetrachloride (TiCl 4 ) In depositing titanium nitride (TiN), which is representative of the metal nitride, it may cause process byproducts such as chlorides to remain in the manufactured thin film, thereby inducing corrosion of metals such as aluminum, and degrading film quality due to the generation of non-volatile byproducts.
Therefore, there is a need to develop a thin film formation method capable of forming a thin film having a complicated structure and a low residual amount of impurities without corroding an interlayer wiring material, and a semiconductor substrate manufactured by the method, and a need to develop a growth regulator which can provide a uniform thickness and step coverage even with a high Aspect ratio (Aspect ratio) due to an increase in the number of stacks of VNANDs of 128 layers, 256 layers, 512 layers, etc., and which is less likely to decompose even when used in combination with a thin film precursor, and thus is excellent in effect.
Prior art literature
Patent literature
Korean laid-open patent No. 2006-0037241
Korean laid-open patent No. 2018-0057059
Disclosure of Invention
Technical problem
In order to solve the above-described conventional problems, an object of the present invention is to provide a metal thin film precursor composition, a thin film formation method using the same, and a semiconductor substrate manufactured by the method, which include a growth regulator that provides a low band gap to significantly improve the film quality of a thin film including the same, suppresses side reactions to properly adjust the thin film growth rate, and removes process byproducts in the thin film to prevent corrosion and degradation, can greatly improve step coverage (step coverage), thickness uniformity of the thin film, and resistivity characteristics even if the thin film is formed on a substrate having a complicated structure, and does not decompose even if it is used in combination with the thin film precursor.
Further, the present invention aims to improve the crystallinity of a thin film to improve the electrical characteristics such as density and resistivity of the thin film.
The above object and other objects of the present invention can be achieved by the present invention described below.
Technical proposal
In order to achieve the above object, the present invention provides a metal thin film precursor composition comprising a thin film precursor compound and a growth regulator,
The film precursor compound includes a compound represented by chemical formula 1,
the growth regulator is a linear, branched, cyclic or aromatic compound represented by chemical formula 2,
chemical formula 1:
M x N n L m
in the chemical formula 1, x is an integer of 1 to 3, M is selected from Li, be, C, P, na, mg, al, si, K, ca, sc, ti, V, cr, mn, fe, co, ni, cu, zn, ga, ge, as, se, rb, sr, Y, zr, nb, mo, te, ru, rh, pd, ag, cd, in, sn, sb, te, ce, nd, sm, eu, gd, tb, dy, ho, er, tm, yb, th, pa, U, cs, ba, la, hf, ta, W, re, os, ir, pt, au, hg, tl, pb, bi, pt, at and Tn, N is an integer of 0 to 8, N is F, cl, br, or I or a ligand formed by combining two or more selected from F, cl, br and I, M is an integer of 0 to 5, L is H, C, N, O, P or S, or a ligand formed by combining two or more selected from H, C, N, O and P,
chemical formula 2:
A n B m X o Y i Z j
in the chemical formula 1, a is carbon, silicon, nitrogen, phosphorus or sulfur, B is hydrogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, X is one or more selected from fluorine (F), chlorine (Cl), bromine (Br) and iodine (I), Y and Z are independently one or more selected from oxygen, nitrogen, sulfur and fluorine and are different from each other, n is an integer of 1 to 15, o is an integer of 1 or more, m is 0 to 2n+1, and I and j are integers of 0 to 3.
The n may be an integer of 1 to 6.
The N may be F, cl or Br, or a ligand composed of two or more kinds selected from F, cl and Br.
The growth regulator may be Cl, br or I, or halogen end group formed by combining more than two kinds of Cl, br or I.
The thin film precursor compound may be one or more selected from the group consisting of compounds represented by chemical formulas 3 to 39.
Chemical formula 3 to chemical formula 20:
formulas 21 to 31:
formulas 32 to 39:
in the chemical formulas 3 to 39, the line is a bond, the point where the bond, which is not marked with other elements, is connected to the bond is carbon, the number of hydrogens satisfying the valence of the carbon is omitted, R ' are hydrogen or alkyl groups having 1 to 5 carbon atoms, respectively, and R ' may be connected to adjacent R '.
The weight ratio of the growth regulator to the film precursor compound may be 1:99 to 99:1.
The growth regulator may be one or more selected from the group consisting of compounds represented by chemical formulas 40 to 60.
Formulas 40 to 60:
in the chemical formulas 40 to 60, the line is a bond, the point where the bond, which is not marked with other elements, is connected to the bond is carbon, and the number of hydrogen satisfying the valence of the carbon is omitted.
The metal film precursor composition may be used in an Atomic Layer Deposition (ALD) process, a Plasma Enhanced Atomic Layer Deposition (PEALD) process, a Chemical Vapor Deposition (CVD) process, or a Plasma Enhanced Chemical Vapor Deposition (PECVD) process.
In addition, the present invention provides a thin film forming method comprising the steps of: the metal thin film precursor composition described above is injected into the chamber and adsorbed to the surface of the loaded substrate.
In addition, the present invention may include the steps of:
i) Vaporizing and adsorbing a growth regulator to a surface of a substrate loaded in the chamber;
ii) purging the interior of the chamber with a purge gas for a first time;
iii) Vaporizing and adsorbing a thin film precursor compound to a surface of the substrate different from the portion to which the growth regulator is adsorbed, or to a terminal end of the growth regulator adsorbed to the substrate, inside the chamber;
iv) purging the interior of the chamber a second time with a purge gas;
v) supplying a reaction gas into the chamber; and
vi) a third purge of the chamber interior with a purge gas.
In addition, the present invention may include the steps of:
i-1) vaporizing the metal thin film precursor composition and adsorbing the thin film precursor compound to a surface different from a portion of the substrate to which the growth regulator is adsorbed, among surfaces of the substrate loaded in the chamber, or binding the thin film precursor compound to an end of the growth regulator adsorbed to the substrate;
ii) purging the interior of the chamber with a purge gas for a first time;
v) supplying a reaction gas into the chamber; and
vi-1) additional purging of the chamber interior with a purge gas.
In addition, the present invention may include the steps of:
i-2) vaporizing and adsorbing the film precursor compounds to the surface of the substrate loaded in the chamber;
ii) purging the interior of the chamber with a purge gas for a first time;
iii-1) vaporizing and adsorbing a growth regulator on a surface of the substrate different from the portion on which the growth regulator is adsorbed, or bonding to the end of the thin film precursor adsorbed on the substrate, inside the chamber;
iv) purging the interior of the chamber a second time with a purge gas;
v) supplying a reaction gas into the chamber; and
vi) a third purge of the chamber interior with a purge gas.
The metal film precursor composition may be transferred into an Atomic Layer Deposition (ALD) chamber, a Chemical Vapor Deposition (CVD) chamber, a Plasma Enhanced Atomic Layer Deposition (PEALD) chamber, or a Plasma Enhanced Chemical Vapor Deposition (PECVD) chamber by a gas flow control (VFC) method, a Direct Liquid Injection (DLI) method, or a liquid transfer system (LDS) method.
The ratio of the growth regulator constituting the metal thin film precursor composition to the in-chamber input amount (mg/cycle) of the thin film precursor compound may be 1:0.1 to 1:20.
The reaction gas may be a reducing agent, nitriding agent or oxidizing agent.
The deposition temperature of the thin film forming method may be 50 to 700 ℃.
The thin film may be an oxide film, a nitride film, or a metal film.
The film may comprise a multilayer structure of two or three layers.
The present invention also provides a semiconductor substrate manufactured by the thin film forming method.
The semiconductor substrate may be a low resistance metal Gate interconnect (low resistive metal Gate interconnects), a high aspect ratio 3D metal-insulator-metal (MIM) capacitor (high aspect ratio D metal-insulator-metal capacitor), a DRAM trench capacitor (DRAM trench capacitor), a 3D Gate-All-Around (GAA), or a 3D NAND.
Advantageous effects
According to the present invention, there is provided a metal thin film precursor composition comprising a growth regulator that regulates a deposition rate to appropriately regulate a thin film growth rate, thereby improving step coverage and film quality even if a thin film is formed on a substrate having a complicated structure.
In addition, a growth regulator for thin film formation is provided, and further a thin film formation method using the same and a semiconductor substrate manufactured by the method are provided, wherein the growth regulator for thin film formation exhibits reaction stability with respect to a thin film precursor compound, and thus, when forming a thin film, an adsorption structure and a growth rate of the thin film precursor compound are regulated and process byproducts are reduced to prevent corrosion and deterioration and improve crystallinity of the thin film, thereby improving resistivity characteristics and electrical characteristics of the thin film.
Drawings
FIG. 1 shows the effect of post injection of the growth regulator according to the invention into MoO 2 Cl 2 Is not used in the experiment of (a) and (b) without using the growth regulatorA graph for comparison of the control group experiments of (a).
FIG. 2 shows the prior injection of the growth regulator according to the present invention into NbF 5 Is compared with a control group experiment without the growth regulator. The left panel shows the secondary ion mass spectrometry depth profile (SIMS depth profile) of the control NbN film, and the right panel shows the secondary ion mass spectrometry depth profile (SIMS depth profile) of the NbN film produced by first implanting the growth regulator set forth in the present invention.
Detailed Description
Hereinafter, the growth regulator, the metal thin film precursor composition, the thin film forming method using the same, and the semiconductor substrate manufactured by the method of the present application will be described in detail.
The inventors of the present application confirmed that, when a metal thin film precursor compound is adsorbed to the surface of a substrate loaded inside a chamber, if the metal thin film precursor compound is adsorbed together with a growth regulator having a predetermined end group and structure, the adsorption structure and growth rate of the thin film precursor compound are regulated and process byproducts are reduced, thus preventing corrosion and deterioration and improving crystallinity of the thin film, thereby greatly improving resistivity characteristics and electrical characteristics of the thin film. Further, it was confirmed that when a composition containing a film precursor compound and a specific growth regulator is adsorbed onto the surface of a substrate loaded in a chamber, or when the film precursor compound is adsorbed first and then the growth regulator is adsorbed on the surface of a substrate loaded in a chamber, the resistivity characteristics are greatly improved, and based on this, the present application has been completed.
As a preferred embodiment, the thin film forming method may include the steps of: i) Vaporizing and adsorbing a growth regulator to a surface of a substrate loaded in the chamber; ii) purging the interior of the chamber with a purge gas for a first time; iii) Vaporizing and adsorbing a thin film precursor compound to a surface of the substrate different from the portion to which the growth regulator is adsorbed, or to a terminal end of the growth regulator adsorbed to the substrate, inside the chamber; iv) purging the interior of the chamber a second time with a purge gas; v) supplying a reaction gas into the chamber; and vi) purging the chamber interior with a purge gas for the third time, at which time the film growth rate is controlled and the generated process by-products are effectively removed even if the deposition temperature is increased at the time of forming the film, thus having advantages of improving the resistivity of the film and greatly improving step coverage.
As another preferred embodiment, the thin film forming method may include the steps of: i-1) vaporizing the metal thin film precursor composition and adsorbing the thin film precursor compound to a surface different from a portion of the substrate to which the growth regulator is adsorbed, among surfaces of the substrate loaded in the chamber, or binding the thin film precursor compound to an end of the growth regulator adsorbed to the substrate; ii) purging the interior of the chamber with a purge gas for a first time; v) supplying a reaction gas into the chamber; and vi-1) additional purging of the chamber interior with a purge gas, at which time the film growth rate is controlled and the generated process by-products are effectively removed even if the deposition temperature is increased at the time of forming the film, thus having advantages of improving the resistivity of the film and greatly improving step coverage.
As another preferred embodiment, the thin film forming method may include the steps of: i-2) vaporizing and adsorbing the film precursor compounds to the surface of the substrate loaded in the chamber; ii) purging the interior of the chamber with a purge gas for a first time; iii-1) vaporizing and adsorbing a growth regulator on a surface of the substrate different from the portion on which the growth regulator is adsorbed, or bonding to the end of the thin film precursor adsorbed on the substrate, inside the chamber; iv) purging the interior of the chamber a second time with a purge gas; v) supplying a reaction gas into the chamber; and vi) purging the chamber interior with a purge gas for the third time, at which time the film growth rate is controlled and the generated process by-products are effectively removed even if the deposition temperature is increased at the time of forming the film, thus having advantages of improving the resistivity of the film and greatly improving step coverage.
The metal film precursor composition comprising the growth regulator and the metal film precursor compound is independently preferably transferred into the chamber in a VFC mode, DLI mode or LDS mode, more preferably in an LDS mode.
The metal film precursor composition comprising the growth regulator and the metal film precursor compound is preferably used in an Atomic Layer Deposition (ALD) process, a Plasma Enhanced Atomic Layer Deposition (PEALD) process, a Chemical Vapor Deposition (CVD) process or a Plasma Enhanced Chemical Vapor Deposition (PECVD) process, more preferably in an Atomic Layer Deposition (ALD) process or a Plasma Enhanced Chemical Vapor Deposition (PECVD) process.
The metal thin film precursor compound may include a compound represented by chemical formula 1, and at this time, has advantages in that the intended effect of the present invention is well achieved and the resistivity of the thin film is improved.
Chemical formula 1:
M x N n L m
in the chemical formula 1, x is an integer of 1 to 3, M may be selected from Li, be, C, P, na, mg, al, si, K, ca, sc, ti, V, cr, mn, fe, co, ni, cu, zn, ga, ge, as, se, rb, sr, Y, zr, nb, mo, te, ru, rh, pd, ag, cd, in, sn, sb, te, ce, nd, sm, eu, gd, tb, dy, ho, er, tm, yb, th, pa, U, cs, ba, la, hf, ta, W, re, os, ir, pt, au, hg, tl, pb, bi, pt, at and Tn, N is an integer of 0 to 8, N is F, cl, br or I, or a ligand formed by combining two or more members selected from F, cl, br and I, M is an integer of 0 to 5, L is H, C, N, O, P or S, or a ligand formed by combining two or more members selected from H, C, N, O and P.
Regarding the metal thin film precursor compound, as an example, in the chemical formula 1, x is an integer of 1 to 2, M may be selected from Li, be, C, P, na, mg, al, si, K, ca, sc, ti, V, cr, mn, fe, co, ni, cu, zn, ga, ge, as, se, rb, sr, Y, zr, nb, mo, te, ru, rh, pd, ag, cd, in, sn, sb, te, ce, nd, sm, eu, gd, tb, dy, ho, er, tm, yb, th, pa, U, cs, ba, la, hf, ta, W, re, os, ir, pt, au, hg, tl, pb, bi, pt, at and Tn, N is an integer of 1 to 8, N is F, cl, br or I, or a ligand composed of two or more selected from F, cl, br and I, M is an integer of 0 to 5, L may be H, C, N, O, P or S, or a ligand composed of two or more selected from H, C, N, O and P, at which time the intended effect of the present invention is well achieved and the advantage of improved resistivity is exhibited.
The n may be an integer of 1 to 7, preferably an integer of 1 to 6, and within this range, there are advantages in that the process by-products are reduced and the adsorption force on the substrate is more excellent. In addition, N is a halogen element, preferably fluorine, chlorine or bromine, more preferably fluorine or chlorine, and within this range, there are advantages that the process by-products are reduced and the adsorption force on the substrate is more excellent. In addition, the N may be chlorine, for example, and in this case, there is an advantage in that the effect of improving the crystallinity of the thin film and reducing the process by-products due to suppression of side reactions is excellent.
As another preferred example, in the chemical formula 1, the N may be iodine or bromine, and in this case, there is an advantage in that it is more suitable for a process requiring low temperature deposition.
As a preferred embodiment, the metal thin film precursor compound may be a branched or cyclic compound represented by chemical formula 1, wherein a is carbon, B is hydrogen or an alkyl group having 1 to 10 carbon atoms, X is bromine (Br) or iodine (I), Y and Z are independently one or more selected from oxygen, nitrogen, sulfur and fluorine and are different from each other, n is an integer of 1 to 15, o is an integer of 1 or more, m is 0 to 2n+1, and I and j are 0, and at this time, there is an advantage that the intended effect of the present invention is well achieved and improved resistivity is exhibited, the film crystallinity is improved and the effect of reducing process by-products due to suppression of side reactions is more excellent.
The metal thin film precursor compound may be a halogen-containing compound, and as a specific example, may be compounds represented by chemical formulas 3 to 39. Among them, the compounds represented by chemical formulas 3 to 39 may be selected independently of each other or they may be used in combination.
Chemical formula 3 to chemical formula 20:
Formulas 21 to 31:
formulas 32 to 39:
in the chemical formulas 3 to 39, the line is a bond, the point where the bond, which is not marked with other elements, is connected to the bond is carbon, the number of hydrogens satisfying the valence of the carbon is omitted, R ' are hydrogen or alkyl groups having 1 to 5 carbon atoms, respectively, and R ' may be connected to adjacent R '.
In addition, the metal thin film precursor composition of the present invention comprises a thin film precursor compound and a growth regulator,
the film precursor compound includes the above-described compound represented by chemical formula 1,
the growth regulator is a linear, branched, cyclic or aromatic compound represented by chemical formula 2, and at this time, has advantages in that the desired effect is well achieved and the resistivity of the thin film is improved.
Chemical formula 2:
A n B m X o Y i Z j
in the chemical formula 1, a is carbon, silicon, nitrogen, phosphorus or sulfur, B is hydrogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, X is one or more selected from fluorine (F), chlorine (Cl), bromine (Br) and iodine (I), Y and Z are independently one or more selected from oxygen, nitrogen, sulfur and fluorine and are different from each other, n is an integer of 1 to 15, o is an integer of 1 or more, m is 0 to 2n+1, and I and j are integers of 0 to 3.
The growth regulator and the film precursor compound may have a weight ratio of 1:99 to 99:1, a weight ratio of 1:90 to 90:1, a weight ratio of 1:85 to 85:1, or a weight ratio of 1:80 to 80:1.
As an example, the growth regulator may be a branched or cyclic compound represented by chemical formula 1, wherein a is carbon or silicon, B is hydrogen, alkyl having 1 to 10 carbon atoms, cycloalkyl having 3 to 10 carbon atoms, or alkoxy having 1 to 10 carbon atoms, X is fluorine (F), chlorine (Cl), bromine (Br), or iodine (I), Y and Z are independently one or more selected from oxygen, nitrogen, sulfur, and fluorine and are different from each other, n is an integer of 1 to 15, o is an integer of 1 or more, m is 0 to 2n+1, and I and j are 0, at which time the intended effect of the present invention is well achieved and has an advantage of improving the resistivity of a thin film.
The X may be a halogen element, preferably fluorine, chlorine, bromine or iodine, more preferably chlorine or bromine, and within this range, there are advantages in that the process by-products are reduced and the adsorption force on the substrate is more excellent. In addition, as an example, the X may be chlorine, which has an advantage of improving crystallinity of the thin film and reducing process by-products due to suppression of side reactions.
As another preferred example, in chemical formula 1, X may be iodine or bromine, and in this case, there is an advantage in that it is more suitable for a process requiring low temperature deposition.
As a preferred embodiment, the growth regulator may be a branched or cyclic compound represented by chemical formula 1, wherein a is carbon, B is hydrogen or an alkyl group having 1 to 10 carbon atoms, X is bromine (Br) or iodine (I), Y and Z are independently one or more selected from oxygen, nitrogen, sulfur and fluorine and are different from each other, n is an integer of 1 to 15, o is an integer of 1 or more, m is 0 to 2n+1, and I and j are 0, at which time, the intended effect of the present invention is well achieved and the advantage of improved resistivity is exhibited.
As a preferred embodiment, the growth regulator may be a branched or cyclic compound represented by chemical formula 1, wherein a is carbon, B is hydrogen or an alkyl group having 1 to 10 carbon atoms, X is bromine (Br) or iodine (I), Y and Z are independently one or more selected from oxygen, nitrogen, sulfur and fluorine and are different from each other, n is an integer of 1 to 15, o is an integer of 1 or more, m is 0 to 2n+1, and I and j are 0, and at this time, there is an advantage in that the intended effect of the present invention is well achieved and improved resistivity is exhibited, the crystallinity of the thin film is improved and the effect of reducing process by-products due to suppression of side reactions is more excellent.
As another preferred embodiment, the growth regulator may include a hydrocarbon having an electron acceptor end group, which may be a substance that is not reactive with the thin film precursor compound, and when the growth regulator is used, an adsorption structure and a growth rate of the thin film precursor compound are adjusted, a process by-product is reduced, and a deposition rate is adjusted to appropriately reduce a thin film growth rate, so that step coverage and film quality can be improved even if a thin film is formed on a substrate having a complicated structure, and corrosion and degradation can be prevented and crystallinity of the thin film can be improved, thereby improving resistivity characteristics and electrical characteristics of the thin film.
The hydrocarbon is preferably a compound having a structure in which one or more electron acceptor end groups are substituted with an electron acceptor end group selected from alkane and cycloalkane, and in this case, there is an advantage that reactivity and solubility are low, moisture is easily managed, and step coverage (step coverage) on a trench structure of a high Aspect ratio (Aspect ratio) is improved when a thin film is formed.
As a more preferred example, the hydrocarbon may include C 1 ～C 10 Alkane (alkine) or C 3 ～C 10 Is preferably C 3 ～C 10 In this case, there is an advantage that the reactivity and solubility are low and the water content can be easily controlled.
In the present application, C 1 、C 3 And the like, represent the number of carbon atoms.
The cycloalkane is preferably C 3 ～C 10 The monocyclic alkane of (2) is liquid at normal temperature and has the highest vapor pressure, and thus is suitable for vapor deposition process, but is not limited thereto.
The term "electron acceptor end group" as used herein, unless otherwise defined, refers to a functional group capable of improving the film quality when combined with a film precursor compound.
As an example, the electron acceptor end groups may be ortho-oriented and para-oriented passivating groups.
The above-mentioned terms "ortho-oriented and para-oriented passivating groups" refer to passivating groups that exhibit orientation to ortho, para positions of a precursor compound having a benzene ring when used, unless otherwise defined.
As another example, the electron acceptor terminal group may be an electron acceptor having an electronegativity (electronegativity) of 2.0 to 4.0, preferably an electron acceptor (electron accepter) having an electronegativity of 2.0 to 3.0.
Unless otherwise limited to the electronegativity, when a precursor compound having no benzene ring is used, a functional group satisfying the electronegativity range may be present.
As a specific example, the electron acceptor terminal group may be a halogen element, preferably fluorine, chlorine, bromine or iodine, more preferably bromine or iodine, and within this range, there are advantages that the effect of reducing process by-products and improving step coverage is more excellent. In addition, as an example, the X may be iodine, and in this case, there is an advantage in that it is more suitable for a process requiring low-temperature deposition. In particular, the X may use an iodine, at which time the impurity content is not excessively increased, and thus is more effective for improving the film quality of the thin film.
As a more preferred embodiment, the growth regulator may contain Cl, br or I, or a halogen end group composed of a combination of two or more selected from Cl, br or I, at which time there is an advantage in that the intended effect of the present invention is well achieved and exhibits improved resistivity, improved film crystallinity and more excellent effect of reducing process by-products due to suppression of side reactions.
As a more preferred embodiment, when the growth regulator has a skeleton of a tertiary carbon cation, there is an advantage in that the effect of preventing impurities remaining after the film is manufactured, particularly, carbon is not remaining more remarkable.
Regarding the reactivity of the hydrocarbon with the thin film precursor compound, the H-NMR spectrum measured before mixing the hydrocarbon and the thin film precursor compound is compared with the nuclear magnetic resonance hydrogen spectrum (H-NMR spectrum) measured after pressurizing the mixture having a molar ratio of 1:1 for 1 hour to generate an NMR peak, and when the integral value at the top of the NMR peak is set as the impurity content, the impurity content (%) is shown to be less than 0.1%, and therefore, when a growth regulator is used, the adsorption structure and growth rate of the thin film precursor compound are regulated, and the process by-products can be reduced, and the deposition rate is regulated to appropriately reduce the growth rate of the thin film, so that even if the thin film is formed on a substrate having a complicated structure, the step coverage and the membranous can be improved, corrosion and deterioration can be prevented, the crystallinity of the thin film can be improved, and thus the resistivity property and the electrical property of the thin film can be improved.
Based on the reactivity described above, the growth regulator has the advantage of easily regulating the viscosity and vapor pressure of the film precursor compound without interfering with the behavior of the film precursor compound.
As an example, the hydrocarbon exhibiting the above-described reactivity and containing the electron acceptor end group may be a linear or branched alkane compound or a cycloalkane compound substituted with halogen.
As a specific example, one or more selected from the group consisting of t-butyl iodide, 1-iodobutane, 2-iodo-3-methylbutane, 3-iodo-2, 4-dimethylpentane, iodocyclohexane, iodocyclopentane, t-butylbromide, 1-bromobutane, 2-bromo-3-methylbutane, 3-bromo-2, 4-dimethylpentane, bromocyclohexane, cyclopentylbromide, t-butylchloride, 1-chlorobutane, 2-chloro-3-methylbutane, 3-chloro-2, 4-dimethylbutane, cyclohexylchloride and cyclopentylchloride is preferable, and one or more selected from the group consisting of t-butyliodide, t-butylbromide, t-butylchloride, 1-iodobutane, 2-iodobutane, 1-bromobutane, 2-bromobutane, 1-chlorobutane and 2-chlorobutane is preferable, and in this case, the by-product of the film precursor compound adsorption structure and growth rate are regulated and the substrate surface is effectively protected (protected) and the substrate is effectively removed as a growth regulator.
As described above, the hydrocarbon may be a halogenated hydrocarbon, and as a specific example, may be compounds represented by chemical formulas 40 to 60. Among them, the compounds represented by chemical formulas 40 to 60 may be independently selected or a mixture thereof may be used.
Formulas 40 to 60:
in the chemical formulas 40 to 60, the line is a bond, the point where the bond, which is not marked with other elements, is connected to the bond is carbon, and the number of hydrogen satisfying the valence of the carbon is omitted.
The metal thin film precursor composition, the metal thin film precursor compound, and the growth regulator are preferably used for an Atomic Layer Deposition (ALD) process, a Plasma Enhanced Atomic Layer Deposition (PEALD) process, a Chemical Vapor Deposition (CVD) process, or a Plasma Enhanced Chemical Vapor Deposition (PECVD) process, and at this time, have advantages of not impeding adsorption of the thin film precursor compound and effectively protecting (protecting) the surface of the substrate as a growth regulator and effectively removing process byproducts.
Preferably, the growth regulator may be liquid at normal temperature (22 ℃) and the density may be 0.8-2.5 g/cm 3 Or 0.8 to 1.7g/cm 3 The vapor pressure (20 ℃) may be 0.1 to 300mmHg or 1 to 300mmHg, and the solubility in water (25 ℃) may be 200mg/L or less, within which the step coverage, the thickness uniformity of the film and the film quality improvement are excellent.
More preferably, the density of the growth regulator may be 0.75 to 2.0g/cm 3 Or 0.8 to 1.7g/cm 3 The vapor pressure (20 ℃) can be 0.1 to 1000mmHg, in waterThe solubility (25 ℃) may be 2000mg/L or less, and in this range, there are excellent effects of step coverage, uniformity of thickness of the film, and improvement of film quality.
In addition, as another preferred example, the thin film forming method of the present invention includes a step of injecting the metal thin film precursor composition into an ALD chamber and adsorbing it to the surface of a loaded substrate, at which time the thin film growth rate is suitably improved and process byproducts generated when forming a thin film are effectively removed, thus having advantages of reducing impurities in the thin film and greatly improving crystallinity.
The thin film forming method may use a reducing agent, a nitriding agent, or an oxidizing agent as a reaction gas.
The deposition temperature of the thin film forming method is, for example, 50 to 700 ℃, preferably 250 to 500 ℃, and more specifically 250 to 450 ℃, 280 to 450 ℃, or 350 to 420 ℃, and in this range, there are advantages that the film resistivity, step coverage, and the like are greatly improved.
In chemical formula 1, the M is titanium, tungsten, molybdenum, silicon, hafnium, zirconium, indium, germanium or niobium, preferably titanium, tungsten, molybdenum or niobium.
In chemical formula 1, N may be a halogen element, preferably fluorine, chlorine, bromine or iodine, more preferably fluorine, chlorine or bromine, and within this range, there are advantages in that process by-products are reduced and the adsorption force on the substrate is more excellent. In addition, the N may be fluorine or chlorine, for example, and in this case, there is an advantage in that the effect of improving the crystallinity of the thin film and reducing the process by-products due to suppression of side reactions is more excellent.
In the chemical formula 1, L may be H, C, N, O, P or S, or a ligand composed of two or more kinds selected from H, C, N, O and P, and in this case, there is an advantage in that the effect of improving the crystallinity of the thin film and reducing the process by-products due to suppression of side reactions is more excellent.
The compound represented by chemical formula 1 is a compound having a halogen functional group on a central metal, and is specifically selected from molybdenum (V) chloride (MoCl) 5 ) Molybdenum tetrachloride (MoOCl) 4 ) Molybdenum dichloride (MoO) 2 Cl 2 ) Molybdenum (VI) fluoride (MoF) 6 ) Tungsten (VI) chloride (WCl) 6 ) Tungsten (VI) fluoride (WF) 6 ) Niobium (V) chloride (NbCl) 5 ) Or niobium (V) fluoride (NbF) 6 ) In this case, the process by-product removal effect is remarkable, the step coverage is improved, and the adsorption effect on the substrate is excellent.
The compound represented by chemical formula 1 is a tertiary alkyl compound substituted with halogen, and as a specific example, is selected from titanium tetrachloride, 2-chloro-3-methyl titanium, 2-chloro-2-methyl titanium, titanium tetrabromide, 3-bromo-3-methyl titanium, titanium tetrachloride, 2-chloro-3-methyl tungsten, 2-chloro-2-methyl tungsten, tungsten tetrabromide, 3-bromo-3-methyl tungsten, molybdenum tetrachloride, 2-chloro-3-methyl molybdenum, 2-chloro-2-methyl molybdenum, molybdenum tetrabromide, 3-bromo-3-methyl molybdenum, hafnium tetrachloride, one or more of 2-chloro-3-methylhafnium, 2-chloro-2-methylhafnium, hafnium tetrabromide, 3-bromo-3-methylhafnium, hafnium tetrachloride, 2-chloro-3-methylzirconium, 2-chloro-2-methylzirconium, zirconium tetrabromide, 3-bromo-3-methylzirconium, indium tetrachloride, 2-chloro-3-methylindium, 2-chloro-2-methylindium, indium tetrabromide, 3-bromo-3-methylindium or 3-bromo-3-methylindium, at this time, the liquid crystal display device, the process by-product removal effect is remarkable, the step coverage is improved, and the adsorption effect on the substrate is excellent.
The compound (or conductive compound) represented by chemical formula 1 is described by way of specific example, but is not limited thereto, and may be any thin film precursor compound conventionally used in an Atomic Layer Deposition (ALD) method.
The term "conductive compound" used in the present invention means a substance which has conductivity due to having an electron donor or acceptor and which is affected according to its structure and oxidation state upon charge movement, unless otherwise defined.
As a specific example, one or more selected from the group consisting of a metal film precursor compound, a metal oxide film precursor compound, a metal nitride film precursor compound, and a silicon nitride film precursor compound may be included, and the metal is preferably one or more selected from the group consisting of tungsten, cobalt, chromium, aluminum, hafnium, vanadium, niobium, germanium, lanthanoid, actinoid, gallium, tantalum, zirconium, ruthenium, copper, titanium, nickel, iridium, molybdenum, platinum, ruthenium, niobium, and iridium.
As an example, the metal film precursor, the metal oxide film precursor, and the metal nitride film precursor may be one or more selected from the group consisting of metal halides, metal alkoxides, metal alkyls, metal amides, metal carbonyls, and substituted or unsubstituted cyclopentadienyl metal compounds, respectively, but are not limited thereto.
As an example, the metal oxide film precursor may be independently selected from PtO, ptO 2 、RuO 2 、IrO 2 、SrRuO 3 、BaRuO 3 CaRuO 3 Is a kind of medium.
As specific examples, the metal film precursor, the metal oxide film precursor, and the metal nitride film precursor may be selected from titanium tetrachloride (titanium tetrachloride), germanium tetrachloride (germanium tetrachloride), tin tetrachloride (tetratrchlorotin), tris (isopropyl) ethylmethylaminogermanium (tris (isopropyl) ethylmethylaminogermanium), tetraethoxygermanium (tetraethoxygermanium), tetramethyltin (tetramethyltin), tetraethyltin (tetraethyltin), diacetylacetontin (bisacetylacetonate tin), trimethylaluminum (trimethylaluminum), tetrakis (dimethylamino) germanium (tetrakis (dimethylamino) germanium), bis (n-butylamino) germanium (germanium) germanium, tetrakis (ethylmethylamino) tin (tetrakis (ethylmethylamino) tin), tetrakis (dimethylamino) tin (tetrakis (dimethylamino) tin), co 2 (CO) 8 ( A dicobaltoctacarbonyl; cobalt octacarbonyl), cp2Co (bisciclopentadienecobalate; cobalt biscyclopentadienyl), co (CO ) 3 ( NO) (cobalt tricarbonyl nitrosyl; cobalt tricarbonyl nitrosyl and CpCo (CO) ) 2 (cabaltdicarbonyl cyclopentadienyl; cyclopentadienyl cobalt dicarbonate), but is not limited thereto.
As an example, the silicon nitride film precursor may be selected from SiH 4 、SiCl 4 、SiF 4 、SiCl 2 H 2 、Si 2 Cl 6 、TEOS、DIPAS、BTBAS、(NH 2 )Si(NHMe) 3 、(NH 2 )Si(NHEt) 3 、(NH 2 )Si(NH n Pr) 3 、(NH 2 )Si(NH i Pr) 3 、(NH 2 )Si(NH n Bu) 3 、(NH 2 )Si(NH i Bu) 3 、(NH 2 )Si(NH t Bu) 3 、(NMe 2 )Si(NHMe) 3 、(NMe 2 )Si(NHEt) 3 、(NMe 2 )Si(NH n Pr) 3 、(NMe 2 )Si(NH i Pr) 3 、(NMe 2 )Si(NH n Bu) 3 、(NMe 2 )Si(NH i Bu) 3 、(NMe 2 )Si(NH t Bu) 3 、(NEt 2 )Si(NHMe) 3 、(NEt 2 )Si(NHEt) 3 、(NEt 2 )Si(NH n Pr) 3 、(NEt 2 )Si(NH i Pr) 3 、(NEt 2 )Si(NH n Bu) 3 、(NEt 2 )Si(NH i Bu) 3 、(NEt 2 )Si(NH t Bu) 3 、(N n Pr 2 )Si(NHMe) 3 、(N n Pr 2 )Si(NHEt) 3 、(N n Pr 2 )Si(NH n Pr) 3 、(N n Pr 2 )Si(NH i Pr) 3 、(N n Pr 2 )Si(NH n Bu) 3 、(N n Pr 2 )Si(NH i Bu) 3 、(N n Pr 2 )Si(NH t Bu) 3 、(N i Pr 2 )Si(NHMe) 3 、(N i Pr 2 )Si(NHEt) 3 、(N i Pr 2 )Si(NH n Pr) 3 、(N i Pr 2 )Si(NH i Pr) 3 、(N i Pr 2 )Si(NH n Bu) 3 、(N i Pr 2 )Si(NH i Bu) 3 、(N i Pr 2 )Si(NH t Bu) 3 、(N n Bu 2 )Si(NHMe) 3 、(N n Bu 2 )Si(NHEt) 3 、(N n Bu 2 )Si(NH n Pr) 3 、(N n Bu 2 )Si(NH i Pr) 3 、(N n Bu 2 )Si(NH n Bu) 3 、(N n Bu 2 )Si(NH i Bu) 3 、(N n Bu 2 )Si(NH t Bu) 3 、(N i Bu 2 )Si(NHMe) 3 、(N i Bu 2 )Si(NHEt) 3 、(N i Bu 2 )Si(NH n Pr) 3 、(N i Bu 2 )Si(NH i Pr) 3 、(N i Bu 2 )Si(NH n Bu) 3 、(N i Bu 2 )Si(NH i Bu) 3 、(N i Bu 2 )Si(NH t Bu) 3 、(N t Bu 2 )Si(NHMe) 3 、(N t Bu 2 )Si(NHEt) 3 、(N t Bu 2 )Si(NH n Pr) 3 、(N t Bu 2 )Si(NH i Pr) 3 、(N t Bu 2 )Si(NH n Bu) 3 、(N t Bu 2 )Si(NH i Bu) 3 、(N t Bu 2 )Si(NH t Bu) 3 、(NH 2 ) 2 Si(NHMe) 2 、(NH 2 ) 2 Si(NHEt) 2 、(NH 2 ) 2 Si(NH n Pr) 2 、(NH 2 ) 2 Si(NH i Pr) 2 、(NH 2 ) 2 Si(NH n Bu) 2 、(NH 2 ) 2 Si(NH i Bu) 2 、(NH 2 ) 2 Si(NH t Bu) 2 、(NMe 2 ) 2 Si(NHMe) 2 、(NMe 2 ) 2 Si(NHEt) 2 、(NMe 2 ) 2 Si(NH n Pr) 2 、(NMe 2 ) 2 Si(NH i Pr) 2 、(NMe 2 ) 2 Si(NH n Bu) 2 、(NMe 2 ) 2 Si(NH i Bu) 2 、(NMe 2 ) 2 Si(NH t Bu) 2 、(NEt 2 ) 2 Si(NHMe) 2 、(NEt 2 ) 2 Si(NHEt) 2 、(NEt 2 ) 2 Si(NH n Pr) 2 、(NEt 2 ) 2 Si(NH i Pr) 2 、(NEt 2 ) 2 Si(NH n Bu) 2 、(NEt 2 ) 2 Si(NH i Bu) 2 、(NEt 2 ) 2 Si(NH t Bu) 2 、(N n Pr 2 ) 2 Si(NHMe) 2 、(N n Pr 2 ) 2 Si(NHEt) 2 、(N n Pr 2 ) 2 Si(NH n Pr) 2 、(N n Pr 2 ) 2 Si(NH i Pr) 2 、(N n Pr 2 ) 2 Si(NH n Bu) 2 、(N n Pr 2 ) 2 Si(NH i Bu) 2 、(N n Pr 2 ) 2 Si(NH t Bu) 2 、(N i Pr 2 ) 2 Si(NHMe) 2 、(N i Pr 2 ) 2 Si(NHEt) 2 、(N i Pr 2 ) 2 Si(NH n Pr) 2 、(N i Pr 2 ) 2 Si(NH i Pr) 2 、(N i Pr 2 ) 2 Si(NH n Bu) 2 、(N i Pr 2 ) 2 Si(NH i Bu) 2 、(N i Pr 2 ) 2 Si(NH t Bu) 2 、(N n Bu 2 ) 2 Si(NHMe) 2 、(N n Bu 2 ) 2 Si(NHEt) 2 、(N n Bu 2 ) 2 Si(NH n Pr) 2 、(N n Bu 2 ) 2 Si(NH i Pr) 2 、(N n Bu 2 ) 2 Si(NH n Bu) 2 、(N n Bu 2 ) 2 Si(NH i Bu) 2 、(N n Bu 2 ) 2 Si(NH t Bu) 2 、(N i Bu 2 ) 2 Si(NHMe) 2 、(N i Bu 2 ) 2 Si(NHEt) 2 、(N i Bu 2 ) 2 Si(NH n Pr) 2 、(N i Bu 2 ) 2 Si(NH i Pr) 2 、(N i Bu 2 ) 2 Si(NH n Bu) 2 、(N i Bu 2 ) 2 Si(NH i Bu) 2 、(N i Bu 2 ) 2 Si(NH t Bu) 2 、(N t Bu 2 ) 2 Si(NHMe) 2 、(N t Bu 2 ) 2 Si(NHEt) 2 、(N t Bu 2 ) 2 Si(NH n Pr) 2 、(N t Bu 2 ) 2 Si(NH i Pr) 2 、(N t Bu 2 ) 2 Si(NH n Bu) 2 、(N t Bu 2 ) 2 Si(NH i Bu) 2 、(N t Bu 2 ) 2 Si(NH t Bu) 2 、Si(HNCH 2 CH 2 NH) 2 、Si(MeNCH 2 CH 2 NMe) 2 、Si(EtNCH 2 CH 2 NEt) 2 、Si( n PrNCH 2 CH 2 N n Pr) 2 、Si( i PrNCH 2 CH 2 N i Pr) 2 、Si( n BuNCH 2 CH 2 N n Bu) 2 、Si( i BuNCH 2 CH 2 N i Bu) 2 、Si( t BuNCH 2 CH 2 N t Bu) 2 、Si(HNCHCHNH) 2 、Si(MeNCHCHNMe) 2 、Si(EtNCHCHNEt) 2 、Si( n PrNCHCHN n Pr) 2 、Si( i PrNCHCHN i Pr) 2 、Si( n BuNCHCHN n Bu) 2 、Si( i BuNCHCHN i Bu) 2 、Si( t BuNCHCHN t Bu) 2 、(HNCHCHNH)Si(HNCH 2 CH 2 NH)、(MeNCHCHNMe)Si(MeNCH 2 CH 2 NMe)、(EtNCHCHNEt)Si(EtNCH 2 CH 2 NEt)、( n PrNCHCHN n Pr)Si( n PrNCH 2 CH 2 N n Pr)、( i PrNCHCHN i Pr)Si( i PrNCH 2 CH 2 N i Pr)、( n BuNCHCHN n Bu)Si( n BuNCH 2 CH 2 N n Bu)、( i BuNCHCHN i Bu)Si( i BuNCH 2 CH 2 N i Bu)、( t BuNCHCHN t Bu)Si( t BuNCH 2 CH 2 N t Bu)、(NH t Bu) 2 Si(HNCH 2 CH 2 NH)、(NH t Bu) 2 Si(MeNCH 2 CH 2 NMe)、(NH t Bu) 2 Si(EtNCH 2 CH 2 NEt)、(NH t Bu) 2 Si( n PrNCH 2 CH 2 N n Pr)、(NH t Bu) 2 Si( i PrNCH 2 CH 2 N i Pr)、(NH t Bu) 2 Si( n BuNCH 2 CH 2 N n Bu)、(NH t Bu) 2 Si( i BuNCH 2 CH 2 N i Bu)、(NH t Bu) 2 Si( t BuNCH 2 CH 2 N t Bu)、(NH t Bu) 2 Si(HNCHCHNH)、(NH t Bu) 2 Si(MeNCHCHNMe)、(NH t Bu) 2 Si(EtNCHCHNEt)、(NH t Bu) 2 Si( n PrNCHCHN n Pr)、(NH t Bu) 2 Si( i PrNCHCHN i Pr)、(NH t Bu) 2 Si( n BuNCHCHN n Bu)、(NH t Bu) 2 Si( i BuNCHCHN i Bu)、(NH t Bu) 2 Si( t BuNCHCHN t Bu)、( i PrNCH 2 CH 2 N i Pr)Si(NHMe) 2 、( i PfNCH 2 CH 2 N i Pr)Si(NHEt) 2 、( i PrNCH 2 CH 2 N i Pr)Si(NH n Pr) 2 、( i PfNCH 2 CH 2 N i Pr)Si(NH i Pr) 2 、( i PrNCH 2 CH 2 N i Pr)Si(NH n Bu) 2 、( i PfNCH 2 CH 2 N i Pr)Si(NH i Bu) 2 、( i PrNCH 2 CH 2 N i Pr)Si(NH t Bu) 2 、( i PrNCHCHN i Pr)Si(NHMe) 2 、( i PrNCHCHN i Pr)Si(NHEt) 2 、( i PrNCHCHN i Pr)Si(NH n Pr) 2 、( i PrNCHCHN i Pr)Si(NH i Pr) 2 、( i PrNCHCHN i Pr)Si(NH n Bu) 2 、( i PrNCHCHN i Pr)Si(NH i Bu) 2 And [ (II) a ] i PrNCHCHN i pr)Si(NH t Bu) 2 But not limited to, one or more of these.
The said n pr represents an n-propyl group and, i pr represents an isopropyl group, and the isopropyl group, n bu represents an n-butyl group and, i bu represents an isobutyl group and is preferably a group, t bu represents tert-butyl.
As a preferred embodiment, the film precursor compound may comprise a compound selected from TiCl 4 、Ti(CpMe 5 )(OMe) 3 、Ti(CpMe 3 )(OMe) 3 、Ti(OMe) 4 、Ti(OEt) 4 、Ti(OtBu) 4 、Ti(CpMe)(OiPr) 3 、TTIP(Ti(OiPr) 4 、TDMAT(Ti(NMe 2 ) 4 )、Ti(CpMe){N(Me 2 ) 3 }、Pt、Ru、Ir、PtO、PtO 2 、RuO 2 、IrO 2 、SrRuO 3 、BaRuO 3 CaRuO 3 In this case, the effect to be achieved by the present invention can be sufficiently obtained.
The titanium tetrahalide is useful as a metal precursor of a composition for forming a thin film. As an example, the titanium tetrahalide may be selected from TiF 4 、TiCl 4 、TiBr 4 TiI 4 More than one of (a), e.g., tiCl 4 It is preferable in terms of economy, but not limited thereto.
As an example, the titanium tetrahalide has excellent thermal stability, does not decompose at normal temperature, and exists in a liquid state, and thus is suitable as a precursor for an Atomic Layer Deposition (ALD) method to deposit a thin film.
As an example, the film precursor compound may be mixed with a nonpolar solvent (except for the type overlapping with the hydrocarbon) and introduced into the chamber, and in this case, there is an advantage that the viscosity and vapor pressure of the film precursor compound can be easily adjusted.
The nonpolar solvent is preferably one or more selected from alkanes and cycloalkanes, and in this case, there is an advantage that it contains an organic solvent having low reactivity and solubility and being easy to manage moisture, and the step coverage is improved even if the deposition temperature is increased at the time of forming a thin film.
As a more preferred example, the nonpolar solvent may include C 1 ～C 10 Alkane (alkine) or C 3 ～C 10 Is preferably C 3 ～C 10 In this case, there is an advantage that the reactivity and solubility are low and the water content can be easily controlled.
In the present application, C 1 、C 3 And the like, represent the number of carbon atoms.
The cycloalkane is preferably C 3 ～C 10 The monocyclic alkane of (2) is liquid at normal temperature and has the highest vapor pressure, and thus is suitable for vapor deposition process, but is not limited thereto.
As an example, the solubility of the nonpolar solvent in water (25 ℃) is 200mg/L or less, preferably 50 to 200mg/L, more preferably 135 to 175mg/L, and within this range, there is an advantage that the reactivity with respect to the film precursor compound is low and the water can be easily controlled.
In the present application, the solubility is not particularly limited based on a measurement method or standard conventionally used in the art to which the present application pertains, and as an example, a saturated solution may be measured by an HPLC method.
The content of the nonpolar solvent may be 5 to 95 wt%, preferably 10 to 90 wt%, more preferably 40 to 90 wt%, and still more preferably 70 to 90 wt%, with respect to the total weight of the film precursor compound and the nonpolar solvent.
When the content of the nonpolar solvent to be charged is greater than the upper limit value, impurities are induced, resulting in an increase in the resistance and the impurity value in the thin film, and when the content of the organic solvent to be charged is less than the lower limit value, the effect of improving step coverage due to the addition of the solvent and the effect of reducing impurities such as chlorine (Cl) ions are insignificant.
Preferably, the compound represented by chemical formula 1 or the conductive compound may be liquid at normal temperature (22 ℃) and the density may be 0.8 to 2.5g/cm 3 Or 0.8 to 1.5g/cm 3 The vapor pressure (20 ℃) may be 0.1 to 300mmHg or 1 to 300mmHg, and within this range, there are excellent effects of step coverage, uniformity of thickness of the film, and improvement of film quality.
More preferably, the density of the compound represented by chemical formula 1 or the conductive compound may be 0.7 to 2.0g/cm 3 Or 0.8-1.8 g/cm 3 The vapor pressure (20 ℃) may be 0.1 to 1000mmHg, and within this range, there are excellent effects of step coverage, uniformity of thickness of the film, and improvement of film quality.
The ratio of the growth regulator to the in-chamber input amount (mg/cycle) of the thin film precursor compound may be 1:0.1 to 1:20, preferably 1:0.2 to 1:15, more preferably 1:0.5 to 1:12, and still more preferably 1:0.7 to 1:10, within which the step coverage improving effect and the process by-product reducing effect are remarkable.
The precursor composition composed of the growth regulator and the film precursor compound is preferably used for an Atomic Layer Deposition (ALD) process, a Plasma Enhanced Atomic Layer Deposition (PEALD) process, a Chemical Vapor Deposition (CVD) process, or a Plasma Enhanced Chemical Vapor Deposition (PECVD) process, and at this time, has advantages of remarkable process by-product reduction effect, excellent step coverage, excellent film density improvement effect, and more excellent electric characteristics of the film.
The thin film forming method of the present invention includes a step of injecting the precursor composition into a chamber and adsorbing it to the surface of a loaded substrate, at this time, it is possible to suppress side reactions and adjust a thin film growth rate at the time of forming a thin film, reduce process byproducts in the thin film to reduce corrosion and degradation, and improve crystallinity of the thin film, thereby greatly improving step coverage and electrical characteristics of the thin film even if the thin film is formed on a substrate having a complicated structure.
In the step of adsorbing the precursor composition to the surface of the substrate, the supply Time (Feeding Time) of the film precursor composition, the metal film precursor compound constituting the film precursor composition, or the growth regulator to the surface of the substrate is preferably 0.01 to 10 seconds, more preferably 0.02 to 5 seconds, still more preferably 0.04 to 3 seconds, still more preferably 0.05 to 2 seconds per cycle, and within this range, there are advantages that the film growth rate is low and the step coverage and economy are excellent.
In the present application, the supply Time (Feeding Time) of the precursor composition is based on the volume of the chamber of 15 to 20L and the flow rate of 0.5 to 100mg/s, more specifically, based on the volume of the chamber of 18L and the flow rate of 1 to 25 mg/s.
As a preferred embodiment, the thin film forming method may include the steps of: i) Vaporizing and adsorbing the precursor composition to a surface of a substrate loaded in a chamber; ii) purging the interior of the chamber with a purge gas for a first time; iii) Supplying a reaction gas into the chamber; and iv) purging the chamber interior a second time with a purge gas. At this time, the steps i) to iv) may be repeated as a unit cycle (cycle) until a thin film of a desired thickness is obtained, and when the growth regulator of the present application is charged together with the thin film precursor compound and adsorbed onto the substrate in one cycle, the process by-products are effectively removed even though deposited at a low temperature, thus having advantages of improving the resistivity of the thin film and greatly improving step coverage.
As a preferred example, the thin film forming method of the present invention can add the growth regulator of the present invention together with the thin film precursor compound and cause it to be adsorbed onto the substrate in one cycle, at which time the thin film growth rate can be appropriately reduced even when the thin film is deposited at a low temperature, thereby greatly reducing process byproducts and greatly improving step coverage, and can increase the crystallinity of the thin film to improve the resistivity of the thin film, and can greatly improve the thickness uniformity of the thin film even when applied to a semiconductor device of a large aspect ratio, thereby ensuring the reliability of the semiconductor device.
As an example, in the film formation method, when the growth regulator is adsorbed while the film precursor compound is deposited, the unit cycle may be repeated 1 to 99,999 times, preferably 10 to 10,000 times, more preferably 50 to 5,000 times, still more preferably 100 to 2,000 times, as needed, and within this range, the thickness of the target film can be obtained and the physical property improving effect including resistivity, which the present invention is intended to achieve, can be sufficiently achieved.
In addition, as shown in examples described later, when the growth regulator is adsorbed before deposition of the thin film precursor compound or adsorbed after deposition of the thin film precursor compound, the physical property improving effect including resistivity, which is achieved when the growth regulator and the thin film precursor compound are simultaneously charged and deposited, can also be achieved.
When the growth regulator and the precursor compound of the thin film are adsorbed onto the substrate together or sequentially, the amount of the purge gas to be introduced into the chamber in the step of purging the precursor composition that is not adsorbed may be 10 to 100,000 times, preferably 50 to 50,000 times, more preferably 100 to 10,000 times, as long as the amount of the purge gas to be introduced into the chamber is sufficient to remove the precursor composition that is not adsorbed, and within this range, the precursor composition that is not adsorbed can be sufficiently removed to uniformly form a thin film and prevent deterioration of the film quality. Wherein the input amounts of the purge gas and the precursor composition are respectively based on a period, and the volume of the precursor composition represents the volume of the vaporized metal film precursor composition vapor.
As a specific example, when the purge gas (per cycle) is injected at a flow rate of 166.6mL/s and an injection time of 3 seconds (sec) in the step of purging the unadsorbed precursor composition after the precursor composition is injected at a flow rate of 1.66mL/s and an injection time of 0.5 seconds (sec) (per cycle), the injection amount of the purge gas is 602 times the injection amount of the metal thin film precursor composition.
In the purge step performed immediately after the reaction gas supply step, the amount of the purge gas to be supplied into the chamber may be 10 to 10,000 times, preferably 50 to 50,000 times, more preferably 100 to 10,000 times, based on the volume of the reaction gas to be supplied into the chamber, and the desired effect can be sufficiently achieved in this range. Wherein the input amounts of the purge gas and the reaction gas are respectively based on one period.
Preferably, the metal film precursor composition and film precursor compound can be moved into an ALD chamber, CVD chamber, PEALD chamber, or PECVD chamber by VFC, DLI, or LDS, more preferably can be transferred into an ALD chamber by LDS.
The ratio of the growth regulator constituting the precursor composition to the in-chamber input amount (mg/cycle) of the thin film precursor compound is preferably 1:0.1 to 1:20, more preferably 1:0.2 to 1:15, still more preferably 1:0.5 to 1:12, and still more preferably 1:0.7 to 1:10, and in this range, the step coverage improving effect and the process by-product reducing effect are remarkable.
For example, when the precursor composition is used in the thin film forming method, the degree of improvement in resistivity (μΩ·em) calculated by equation 1 is-50% or less, preferably-50% to-10%, and within this range, the step coverage, the resistivity property, and the film thickness uniformity are excellent.
Mathematical formula 1:
resistivity improvement (%) = [ (resistivity when a growth regulator is used-resistivity when a growth regulator is not used)/resistivity when a growth regulator is not used ] ×100
In equation 1, the degree of improvement in resistivity when the growth regulator is used and when the growth regulator is not used indicates the respective conductive characteristics, that is, resistivity (μΩ·cm), which can be obtained based on the thickness value of the thin film after measuring the sheet resistance by the four-probe method (four-point probe), for example.
In the formula 1, "when the growth regulator is used" means that the growth regulator is adsorbed to the substrate together with the film precursor compound in the film deposition process to manufacture the film, and "when the growth regulator is not used" means that the growth regulator is not used in the film deposition process but the film precursor compound is adsorbed to the substrate to manufacture the film.
As to the film forming method, toThe residual halogen intensity (c/s) in the film measured by XPS may be 100,000 or less, preferably 90,000 or less, more preferably 80,000 or less, still more preferably 76,000 or less, based on the film thickness of (10 nm), and in this range, the effect of preventing corrosion and deterioration is excellent.
As to the film forming method, toThe residual halogen intensity (c/s) in the film measured by secondary ion mass spectrometry (Secondary Ion Mass Spectrometry; SIMS) may be 100,000 or less, preferably 90,000 or less, more preferably 80,000 or less, still more preferably 76,000 or less, based on the film thickness of (10 nm), and within this range, the effect of preventing corrosion and deterioration is excellent.
In the present application, the purge may be 1,000 to 50,000sccm (Standard Cubic Centimeter per Minute; standard milliliters/minute), preferably 2,000 to 30,000sccm, more preferably 2,500 to 15,000sccm, within which the film growth rate per cycle is properly controlled and deposition is performed in a single atomic layer (atomic mono-layer) or in close proximity thereto, thus having an advantage advantageous in terms of film quality.
The ALD (atomic layer deposition) or PEALD (plasma enhanced atomic layer deposition) is very advantageous for manufacturing integrated circuits (IC: integrated Circuit) requiring a high aspect ratio, and in particular, has advantages such as excellent step coverage (uniformity), uniform coverage (uniformity), and precise thickness control based on a self-limiting thin film growth mechanism.
As an example, the thin film formation method may be performed at a deposition temperature in the range of 50 to 700 ℃, preferably at a deposition temperature in the range of 300 to 700 ℃, more preferably at a deposition temperature in the range of 400 to 650 ℃, and even more preferably at a deposition temperature in the range of 400 to 600 ℃, and has an effect of exhibiting ALD process characteristics and growing a thin film excellent in film quality.
As an example, the thin film formation method may be performed at a deposition pressure in the range of 0.01 to 20Torr, preferably at a deposition pressure in the range of 0.1 to 20Torr, more preferably at a deposition pressure in the range of 0.1 to 10Torr, and most preferably at a deposition pressure in the range of 0.1 to 7Torr, and the thin film having a uniform thickness is obtained in this range.
In the present application, the deposition temperature and deposition pressure may be measured temperature and pressure formed in the deposition chamber or measured temperature and pressure applied to the substrate in the deposition chamber.
Preferably, the thin film forming method may include the steps of: heating the temperature in the chamber to a deposition temperature prior to the film precursor composition or a growth regulator or metal film precursor compound comprising the film precursor composition being introduced into the chamber; and/or injecting an inert gas into the chamber for purging prior to the precursor composition being introduced into the chamber.
Further, as a thin film manufacturing apparatus for carrying out the thin film manufacturing method, the thin film manufacturing apparatus of the present invention may include: an ALD chamber; a first vaporizer for vaporizing the growth regulator; a first transfer unit transferring the vaporized growth regulator into the ALD chamber; a second vaporizer that vaporizes the film precursor compound; and a second transfer unit transferring the vaporized thin film precursor compound into the ALD chamber.
In addition, in the present invention, the thin film manufacturing apparatus may include a mixing unit for mixing the vaporized growth regulator with the vaporized thin film precursor compound to pre-mix the precursor composition and then transferred into the chamber.
The chamber, vaporizer, transfer unit, or mixing unit may be any chamber, vaporizer, transfer unit, or mixing unit conventionally used in the art to which the present invention pertains.
As a specific example, the thin film formation method using the ALD process described above is described below.
First, a substrate on which a thin film is to be formed is placed in a deposition chamber in which atomic layer deposition is possible.
The substrate may include a silicon substrate, a silicon oxide, or the like semiconductor substrate.
The substrate may be further formed with a conductive layer or an insulating layer at an upper portion thereof.
The growth regulator and the film precursor compound described above or a mixture thereof with a nonpolar solvent are prepared, respectively, to deposit a film on a substrate placed in the deposition chamber.
Thereafter, it is converted into a vapor phase after being injected into a vaporizer, respectively, and sequentially transferred to a deposition chamber to be adsorbed onto a substrate, or a thin film-forming composition is prepared in advance, and then converted into a vapor phase by using a vaporizer and transferred to a deposition chamber to be adsorbed onto a substrate, followed by purging (purging) to remove the precursor composition (thin film-forming composition) that is not adsorbed.
According to an embodiment of the present application, since a growth regulator that does not react with the metal thin film precursor compound is used, the growth regulator can be mostly removed when purging is performed.
In the present application, as an example, a method of transferring a growth regulator, a metal thin film precursor compound, or the like (composition for forming a thin film) to a deposition chamber may be a gas flow control (Vapor Flow Control; VFC) method of transferring a volatile gas by a gas flow control (Mass Flow Controller; MFC) method or a liquid transfer system (Liquid Delivery System; LDS) method of transferring a liquid by a liquid flow control (Liquid Mass Flow Controller; LMFC) method, and an LDS method is preferable.
In this case, a carrier gas or a diluent gas selected from argon (Ar) and nitrogen (N) may be used for transferring the growth regulator, the metal thin film precursor compound, and the like onto the substrate 2 ) One or a mixture of two or more of helium (He), but is not limited thereto.
In the present application, as an example, an inert gas, preferably the carrier gas or the diluent gas, may be used as the purge gas.
Next, a reaction gas is supplied. The reaction gas may be any reaction gas conventionally used in the art to which the present application pertains, and preferably includes a reducing agent, a nitriding agent, or an oxidizing agent. The reducing agent reacts with the film precursor compound adsorbed on the substrate to form a metal film, the nitriding agent forms a metal nitride film, and the oxidizing agent forms a metal oxide film.
Preferably, the reducing agent may be ammonia (NH 3 ) Or hydrogen (H) 2 ) The nitriding agent may be nitrogen (N) 2 ) Hydrazine gas (N) 2 H 4 ) Or a mixture of nitrogen and hydrogen, the oxidant may be selected from H 2 O、H 2 O 2 、O 2 、O 3 N 2 One or more of O.
Next, the unreacted residual reaction gas is purged with an inert gas. Thereby not only removing the reaction gas but also removing the by-products generated.
As described above, the thin film forming method may repeat the unit cycle of the step of adsorbing the precursor composition onto the substrate, the step of purging the precursor composition that is not adsorbed, the step of supplying the reaction gas, and the step of purging the residual reaction gas as a unit cycle, so as to form a thin film of a desired thickness.
As another example, the thin film forming method may repeat the unit cycle of the step of adsorbing the metal thin film precursor compound on the substrate, the step of purging the metal thin film precursor compound that is not adsorbed, the step of adsorbing the growth regulator on the substrate, the step of purging the growth regulator that is not adsorbed or physically adsorbed, the step of supplying the reaction gas, and the step of purging the residual reaction gas as a unit cycle to form the thin film of a desired thickness.
As another example, the thin film forming method may repeat the unit cycle of the step of adsorbing the growth regulator on the substrate, the step of purging the growth regulator that is not adsorbed, the step of adsorbing the metal thin film precursor compound on the substrate, the step of purging the metal thin film precursor compound that is not adsorbed and the growth regulator that is physically adsorbed, the step of supplying the reaction gas, and the step of purging the residual reaction gas as a unit cycle to form the thin film of a desired thickness.
For example, the unit cycle may be repeated 1 to 99,999 times, preferably 10 to 1,000 times, more preferably 50 to 5,000 times, and still more preferably 100 to 2,000 times, and in this range, the effect of exhibiting the target film characteristics is exhibited well.
The present application also provides a semiconductor substrate manufactured by the thin film forming method of the present application, which has the effect that the step coverage of the thin film, the thickness uniformity of the thin film, and the resistivity property are excellent and the density and the electrical property of the thin film are excellent.
The film produced as described above preferably has a thickness of 30nm or less, a resistivity value of 5 to 2000 mu Ω·cm, a halogen content of 10,000ppm or less, and a step coverage of 80% or more, based on a film thickness of 10nm, and in this range, has an effect of excellent performance as a diffusion preventing film, dielectric film or insulating film and reduction in corrosion of a metal wiring material, but is not limited thereto.
For example, the thickness of the thin film may be 1 to 30nm, preferably 2 to 27nm, more preferably 3 to 25nm, still more preferably 5 to 23nm, and in this range, the effect of excellent thin film characteristics is exhibited.
For example, the specific resistance of the film may be 5 to 2000. Mu. Ω. Cm, preferably 5 to 1900. Mu. Ω. Cm, based on a film thickness of 10nm, and in this range, the film has an excellent effect of film characteristics.
The halogen content of the film analyzed by X-ray photoelectron spectroscopy (X-ray Photoelectron Spectroscopy; XPS) is preferably 10,000ppm or less or 0.001 to 8,000ppm, more preferably 0.001 to 5,000ppm, still more preferably 0.001 to 1000ppm, within which the film has excellent film characteristics and corrosion of the metal wiring material is reducedLess effect. Wherein, as an example, the halogen remained in the film can be Cl 2 Cl or Cl - The lower the halogen residual amount in the film, the more excellent the film quality.
In addition, regarding the film, toThe residual halogen intensity (c/s) in the film measured by secondary ion mass spectrometry (Secondary Ion Mass Spectrometry; SIMS) may be 100,000 or less, preferably 90,000 or less, more preferably 80,000 or less, still more preferably 76,000 or less, based on the film thickness of (10 nm), and within this range, the effect of preventing corrosion and deterioration is excellent. Wherein, as an example, the halogen remained in the film may be F 2 F or F - The lower the halogen residual amount in the film, the more excellent the film quality. />
As an example, the step coverage of the thin film may be 80% or more, preferably 90% or more, and more preferably 95% or more, and within this range, there is an advantage in that the thin film is easily deposited on a substrate even if the thin film structure is complicated, and thus the thin film can be applied to next-generation semiconductor devices.
Taking molybdenum as an example, the film may include a film selected from molybdenum film, molybdenum nitride film (Mo x N y Wherein 0 < x.ltoreq.1.2, 0 < y.ltoreq.1.2, preferably 0.8.ltoreq.x.ltoreq. 1,0.8.ltoreq.y.ltoreq.1, more preferably 1, respectively) and a molybdenum oxide film (Mo z O w Wherein 0 < x.ltoreq.1.2, 0 < y.ltoreq.1.2, preferably 0.8.ltoreq.x.ltoreq. 1,0.8.ltoreq.y.ltoreq.1, more preferably 1) each, preferably comprising a molybdenum nitride film, in which case there is an advantage of being suitable for use as a diffusion preventing film, an etching stopper film or a wiring (electrode) of a semiconductor device.
As another example, when an oxidizing agent including oxygen or ozone is used as a reaction gas for the thin film to be produced, a thin film represented by chemical formula 61 may be formed.
Chemical formula 61:
(M 1-a M″ a )O b
in the chemical formula 61, a is 0.ltoreq.a < 1, b is 0.ltoreq.b.ltoreq.2, and M may be selected from group IV or titanium (Ti), zirconium (Zr), hafnium (Hf), silicon (Si), germanium (Ge), tin (Sn), strontium (Sr), niobium (Nb), barium (Ba) or tantalum (Ta) atoms.
As an example, the film may have a multilayer structure of two or three layers as needed. As a specific example, the multilayer film of the two-layer structure may be a lower-layer-middle-layer structure, and as a specific example, the multilayer film of the three-layer structure may be a lower-layer-middle-layer-upper-layer structure.
As an example, the underlayer film may be a dielectric film, and may contain SiO selected from 2 、MgO、Al 2 O 3 、CaO、ZrSiO 4 、ZrO 2 、HfSiO 4 、Y 2 O 3 、HfO 2 、LaLuO 2 、LaAlO 3 、BaZrO 3 、SrZrO 3 、SrTiO 3 、BaTiO 3 、Si 3 N 4 、SrO、La 2 O 3 、Ta 2 O 5 、BaO、TiO 2 More than one of them.
As an example, the interlayer film may comprise Ti x N y TiN is preferred.
As an example, the upper film may include one or more selected from W, mo.
The following preferred embodiments and drawings are set forth below to aid in understanding the present invention, and are merely examples of the present invention, and it is apparent to those skilled in the art that various changes and modifications can be made within the scope and technical spirit of the present invention, and that such changes and modifications fall within the scope of the appended claims.
Examples
Examples 1 to 5, comparative examples 1 to 3, and reference examples 1 to 2
The combinations shown in table 1 were selected as the growth regulators and metal thin film precursor compounds to be used in examples 1 to 5, comparative examples 1 to 3, and reference examples 1 to 2 below.
Table 1:
| metal film precursor compounds | Growth regulator |
| MoO 2 Cl 2 | Tert-butyl iodide |
| MoO 2 Cl 2 | Diiodomethane |
| MoO 2 Cl 2 | 1-iodobutane |
| MoO 2 Cl 2 | 2-iodobutane |
| MoO 2 Cl 2 | Cyclohexyl iodine |
| MoO 2 Cl 2 | 2-iodo-2-methylpentane |
| MoO 2 Cl 2 | 1-bromo-1-methylcyclohexane |
| MoO 2 Cl 2 | 3-iodo-2, 4-dimethylpentane |
| MoO 2 Cl 2 | Aniline |
| MoO 2 Cl 2 | N-methylaniline |
| MoO 2 Cl 2 | N, N-dimethylaniline |
| MoO 2 Cl 2 | Acetonitrile |
| MoO 2 Cl 2 | Diethyl ether |
| MoO 2 Cl 2 | Anisole (anisole) |
| MoO 2 Cl 2 | Dimethyl sulfide |
| MoO 2 Cl 2 | 3-ethyl-2-pentene |
| MoO 2 Cl 2 | 1,2, 3-trichloropentane |
Examples 1 to 3
Preparation of tert-butyl iodide as growth regulator and MoO as film precursor compound among the compounds shown in Table 1 2 Cl 2 . The prepared growth regulator and the film are put in frontAfter the bulk compounds were separately charged into cans (canster), they were fed at room temperature to a vaporizer heated to 150℃at a flow rate of 0.05g/min by a liquid mass flow controller (Liquid Mass FlowController; LMFC).
After the growth regulator and the thin film precursor compound vaporized into vapor phase in the vaporizer were respectively charged into the deposition chamber loaded with the substrate at a charge ratio of 1:1 for 1 second, argon gas was supplied at 5000sccm for 2 seconds to perform argon purging. At this time, the pressure in the reaction chamber was controlled to 2.5Torr.
Next, ammonia gas as a reactive gas was charged into the reaction chamber at 1000sccm for 3 seconds, followed by argon purging for 3 seconds. At this time, the substrate on which the metal thin film is to be formed is heated at the temperature shown in table 2. This process was repeated 200 to 400 times to form a MoN thin film having a thickness of 10nm as a self-limiting atomic layer.
Comparative examples 1 to 3
The same procedure as in examples 1 to 3 was repeated except that the growth regulators in examples 1 to 3 were not included.
As a result, a MoN thin film having a thickness of 10nm as a self-limiting atomic layer was formed.
Example 4
The same process as in example 1 was repeated except that in example 1, after the growth regulator and the thin film precursor compound vaporized into vapor phase in the vaporizer were sequentially and separately charged into the deposition chamber on which the substrate was mounted at a charge ratio of 1:1 for 1 second, argon gas was supplied at 5000sccm for 2 seconds to perform argon purging.
Specifically, after the growth regulator vaporized into the vapor phase in the vaporizer was put into the deposition chamber loaded with the substrate for 1 second, argon gas was supplied at 5000sccm for 2 seconds to perform argon purging, and then, after the metal thin film precursor compound vaporized into the vapor phase in the vaporizer was put into the deposition chamber loaded with the substrate for 1 second, argon gas was supplied at 5000sccm for 2 seconds to perform argon purging.
As a result, a MoN thin film having a thickness of 10nm as a self-limiting atomic layer was formed by repeating 200 to 400 times.
Example 5
The same process as in example 1 was repeated except that in example 1, after the growth regulator and the thin film precursor compound vaporized into vapor phase in the vaporizer were sequentially and separately charged into the deposition chamber on which the substrate was mounted at a charge ratio of 1:1 for 1 second, argon gas was supplied at 5000sccm for 2 seconds to perform argon purging.
Specifically, after a metal thin film precursor compound vaporized into a vapor phase in a vaporizer was charged into a deposition chamber loaded with a substrate for 1 second, argon gas was supplied at 5000sccm for 2 seconds to perform argon purging, and then, after a growth regulator vaporized into a vapor phase in a vaporizer was charged into a deposition chamber loaded with a substrate for 1 second, argon gas was supplied at 5000sccm for 2 seconds to perform argon purging.
As a result, a MoN thin film having a thickness of 10nm as a self-limiting atomic layer was formed by repeating 200 to 400 times.
Reference example 1
The same process as in example 1 was repeated except that 3-iodobutane was used as a growth regulator instead of t-butyliodide in example 1.
As a result, a MoN thin film having a thickness of 10nm as a self-limiting atomic layer was formed.
Experimental example
1) Deposition evaluation (deposition rate per cycle, GPC)
For the produced film, the thickness of the film was measured using an Ellipsometer (Ellipsometer), which is a device capable of measuring optical characteristics such as thickness or refractive index of the film using polarization characteristics of light, divided by the number of cycles, and the thickness of the film deposited per cycle was calculated to evaluate the deposition rate, and the results thereof are shown in table 2.
2) Evaluation of sheet resistance (resistivity)
After measuring the surface resistance of the manufactured film by a four-probe method (four-point probe) to find the surface resistance, a resistivity value is calculated based on the thickness value of the film.
The degree of improvement in the resistivity (μΩ·cm) was calculated according to equation 1.
Mathematical formula 1:
resistivity improvement (%) = [ (resistivity when a precursor composition is used-resistivity when a growth regulator is not used)/resistivity when a growth regulator is not used ] ×100
Table 2:
as shown in table 2, when the tertiary butyl iodide of the present invention was used as a growth regulator together with a thin film precursor compound (examples 1 to 3) provided the same or similar deposition rate and the resistivity was reduced to 919 to 1884 μΩ·em, compared with when the growth regulator was not used (comparative examples 1 to 3), and therefore, it was confirmed that the thin film growth rate was properly controlled, thereby improving the electrical characteristics.
3) Impurity reduction characteristics
X-ray photoelectron spectroscopy (X-ray Photoelectron Spectroscopy; XPS) analysis was performed on titanium (Ti), nitrogen (N), cl (chlorine), carbon (C) and oxygen (O) elements to compare the reduction characteristics of the process by-products, which are impurities in the produced thin film having a thickness of 10nm, and the results are shown in Table 3.
Table 3:
as shown in table 3, it was confirmed that when the growth regulator of the present invention was used together with the thin film precursor compound (example 1), not only the same or similar level was exhibited as compared with the case where the growth regulator was not used (comparative example 1), but also the Cl and C intensities were reduced to the order of 0.01% as compared with the case where the other growth regulator was used (reference example 1), and therefore, the impurity reduction characteristics were excellent.
In particular, it was confirmed that comparative example 1 was not charged with the growth regulator, and therefore, it should theoretically be impossible to detect carbon, but it was detected that CO and/or CO suspected to originate from the film precursor compound, the purge gas, and the reaction gas were contained 2 However, in example 1 of the present invention, although a growth regulator was added as a hydrocarbon at the time of depositing a thin film, the carbon strength was lower than that of comparative example 1, which indicates that the growth regulator of the present invention is excellent in impurity reduction characteristics.
In particular, it was confirmed that, although the compound having a halide structure similar to the growth regulator of the present invention was added in reference example 1, the impurity intensity was too high compared to example 1 or comparative example 1, and thus the effect of improving the film quality was not exhibited.
In addition, in order to confirm the injection effect of the growth regulator in each step, the following experiment was further performed.
Additional example 1
Using MoO 2 Cl 2 ALD deposition evaluation was performed as a Mo precursor by a VFC supply method.
MoO 2 Cl 2 The pot heating temperature of (2) was 90℃and was carried out at a deposition evaluation temperature of 380 ℃, 400 ℃ and 420 ℃. The process pressure was 6torr and the flow rates of the ammonia reactive gas and the Ar purge gas were 1000sccm.
To confirm the resistivity and GPC improvement effect, a comparison was made in such a manner that a MoN film was deposited.
Specifically, after the post-injection experiment and the pre-injection experiment, respectively, in which the resistivity and the deposition rate were measured in the manner set forth in the previous experimental example, and the resistivity and the deposition rate were also measured in the same manner for the MoN thin film manufactured as the control group in such a manner that the input of the growth regulator was omitted, wherein the post-injection experiment was performed after the injection of MoO 2 Cl 2 Then, ar is purged, tert-butyl iodide is then injected, ar is injected, NH is injected 3 Reaction gas is then injected with Ar to perform ALD deposition experiments, the injection is performed firstThe test is changed to the injection of tertiary butyl iodide, ar and MoO 2 Cl 2 Ar is injected, then NH is injected 3 And (3) injecting Ar into the reaction gas to perform an ALD deposition experiment.
The respective measurement results are shown in fig. 1.
FIG. 1 shows the effect of post injection of the growth regulator according to the invention into MoO 2 Cl 2 A graph comparing the experiment with a control experiment without growth regulator.
As shown in fig. 1, the resistivity was reduced by 35% and the deposition rate was increased by 34% compared to the control group.
Although specific measurement results are not attached, it was confirmed that the injection of t-butyl iodide as a growth regulator before injection is more excellent in improving the resistivity than the injection after injection.
Additional example 2
Except that NbF was used in the additional example 1 5 Replacement of MoO 2 Cl 2 The same process as in the additional example 1 was repeated except that an NbN thin film was manufactured.
The respective measurement results are shown in table 4 and fig. 2.
Table 4 and FIG. 2 show the prior injection of the growth regulator according to the present invention into NbF 5 A graph comparing the experiment with a control experiment without growth regulator.
As shown in table 4 and fig. 2, it was confirmed by SIMS analysis that the F impurity (impurity) and the C impurity (impurity) were improved as compared with the control NbN film.
Table 4:
| category(s) | Control group | NbN (injection first) |
| F intensity (intensity) (c/s) | 116.925 | 75.197 |
| C intensity (intensity) (C/s) | 1,466 | 656 |
Claims (16)
1. A metal film precursor composition characterized in that,
comprising a film precursor compound and a growth regulator,
The film precursor compound includes a compound represented by chemical formula 1,
the growth regulator is a linear, branched, cyclic or aromatic compound represented by chemical formula 2,
chemical formula 1:
M x N n L m
in the chemical formula 1, x is an integer of 1 to 3, M is selected from Li, be, C, P, na, mg, al, si, K, ca, sc, ti, V, cr, mn, fe, co, ni, cu, zn, ga, ge, as, se, rb, sr, Y, zr, nb, mo, te, ru, rh, pd, ag, cd, in, sn, sb, te, ce, nd, sm, eu, gd, tb, dy, ho, er, tm, yb, th, pa, U, cs, ba, la, hf, ta, W, re, os, ir, pt, au, hg, tl, pb, bi, pt, at and Tn, N is an integer of 0 to 8, N is F, cl, br or I, or a ligand formed by combining two or more selected from F, cl, br and I, M is an integer of 0 to 5, L is H, C, N, O, P or S, or a ligand formed by combining two or more selected from H, C, N, O and P,
chemical formula 2:
A n B m X o Y i Z j
in the chemical formula 1, a is carbon, silicon, nitrogen, phosphorus or sulfur, B is hydrogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, X is one or more selected from fluorine (F), chlorine (Cl), bromine (Br) and iodine (I), Y and Z are independently one or more selected from oxygen, nitrogen, sulfur and fluorine and are different from each other, n is an integer of 1 to 15, o is an integer of 1 or more, m is 0 to 2n+1, and I and j are integers of 0 to 3.
2. A metal film precursor composition according to claim 1 wherein,
in the chemical formula 1, n is an integer of 1 to 6.
3. A metal film precursor composition according to claim 1 wherein,
in the chemical formula 1, N is F, cl or Br, or a ligand composed of two or more kinds selected from F, cl and Br.
4. A metal film precursor composition according to claim 1 wherein,
the growth regulator has Cl, br or I, or has a halogen end group formed by combining two or more selected from Cl, br or I.
5. A metal film precursor composition according to claim 1 wherein,
is one or more selected from the group consisting of compounds represented by chemical formulas 40 to 60,
formulas 40 to 60:
in the chemical formulas 40 to 60, the line is a bond, the point where the bond, which is not marked with other elements, is connected to the bond is carbon, and the number of hydrogen satisfying the valence of the carbon is omitted.
6. A metal film precursor composition according to claim 1 wherein,
the metal film precursor composition is used in an Atomic Layer Deposition (ALD) process, a Plasma Enhanced Atomic Layer Deposition (PEALD) process, a Chemical Vapor Deposition (CVD) process, or a Plasma Enhanced Chemical Vapor Deposition (PECVD) process.
7. A film forming method comprising the steps of:
a metal film precursor composition according to claim 1 is injected into the chamber and adsorbed to the surface of the loaded substrate.
8. The method of forming a thin film according to claim 7, comprising the steps of:
i) Vaporizing and adsorbing a growth regulator to a surface of a substrate loaded in the chamber;
ii) purging the interior of the chamber with a purge gas for a first time;
iii) Vaporizing and adsorbing a thin film precursor compound to a surface of the substrate different from the portion to which the growth regulator is adsorbed, or to a terminal end of the growth regulator adsorbed to the substrate, inside the chamber;
iv) purging the interior of the chamber a second time with a purge gas;
v) supplying a reaction gas into the chamber; and
vi) a third purge of the chamber interior with a purge gas.
9. The method of forming a thin film according to claim 7, comprising the steps of:
i-1) vaporizing the metal thin film precursor composition and adsorbing the thin film precursor compound to a surface different from a portion of the substrate to which the growth regulator is adsorbed, among surfaces of the substrate loaded in the chamber, or binding the thin film precursor compound to an end of the growth regulator adsorbed to the substrate;
ii) purging the interior of the chamber with a purge gas for a first time;
v) supplying a reaction gas into the chamber; and
vi-1) additional purging of the chamber interior with a purge gas.
10. The method of forming a thin film according to claim 7, comprising the steps of:
i-2) vaporizing and adsorbing the film precursor compounds to the surface of the substrate loaded in the chamber;
ii) purging the interior of the chamber with a purge gas for a first time;
iii) Vaporizing and adsorbing a growth regulator on a surface of the substrate different from the portion on which the growth regulator is adsorbed, or bonding to an end of a thin film precursor adsorbed on the substrate, inside the chamber;
iv) purging the interior of the chamber a second time with a purge gas;
v) supplying a reaction gas into the chamber; and
vi) a third purge of the chamber interior with a purge gas.
11. The method for forming a thin film according to claim 7, wherein,
the metal film precursor composition is transferred into an Atomic Layer Deposition (ALD) chamber, a Chemical Vapor Deposition (CVD) chamber, a Plasma Enhanced Atomic Layer Deposition (PEALD) chamber, or a Plasma Enhanced Chemical Vapor Deposition (PECVD) chamber by a VFC method, a DLI method, or an LDS method.
12. The method for forming a thin film according to any one of claim 7 to 10, wherein,
the reaction gas is a reducing agent, a nitriding agent or an oxidizing agent.
13. The method for forming a thin film according to claim 7, wherein,
the deposition temperature of the film forming method is 50-700 ℃.
14. The method for forming a thin film according to claim 7, wherein,
the film is an oxide film, a nitride film or a metal film.
15. The method for forming a thin film according to claim 7, wherein,
the film comprises a multilayer structure of two or three layers.
16. A semiconductor substrate, characterized in that,
manufactured by the thin film forming method according to claim 7.
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