WO2022169290A1 - 하프늄 전구체 화합물, 이를 포함하는 하프늄 함유 막 형성용 조성물 및 하프늄-함유 막 형성 방법 - Google Patents
하프늄 전구체 화합물, 이를 포함하는 하프늄 함유 막 형성용 조성물 및 하프늄-함유 막 형성 방법 Download PDFInfo
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- WO2022169290A1 WO2022169290A1 PCT/KR2022/001746 KR2022001746W WO2022169290A1 WO 2022169290 A1 WO2022169290 A1 WO 2022169290A1 KR 2022001746 W KR2022001746 W KR 2022001746W WO 2022169290 A1 WO2022169290 A1 WO 2022169290A1
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- hafnium
- film
- group
- iso
- containing film
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- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 title claims abstract description 149
- 229910052735 hafnium Inorganic materials 0.000 title claims abstract description 148
- 239000002243 precursor Substances 0.000 title claims abstract description 83
- 150000001875 compounds Chemical class 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 56
- 239000000203 mixture Substances 0.000 title claims abstract description 22
- 238000000231 atomic layer deposition Methods 0.000 claims description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 7
- 150000004767 nitrides Chemical class 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 5
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 5
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 5
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 4
- 238000005229 chemical vapour deposition Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 claims description 3
- DIIIISSCIXVANO-UHFFFAOYSA-N 1,2-Dimethylhydrazine Chemical compound CNNC DIIIISSCIXVANO-UHFFFAOYSA-N 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000010408 film Substances 0.000 description 76
- 239000010409 thin film Substances 0.000 description 52
- 239000000758 substrate Substances 0.000 description 24
- 238000000151 deposition Methods 0.000 description 14
- 230000008021 deposition Effects 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 10
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 10
- 239000004065 semiconductor Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- -1 2,2,4-trimethylpentyl group Chemical group 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000007983 Tris buffer Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 229910000449 hafnium oxide Inorganic materials 0.000 description 5
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 235000012431 wafers Nutrition 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 229940043279 diisopropylamine Drugs 0.000 description 4
- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- 238000010926 purge Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- NJBCRXCAPCODGX-UHFFFAOYSA-N 2-methyl-n-(2-methylpropyl)propan-1-amine Chemical compound CC(C)CNCC(C)C NJBCRXCAPCODGX-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- PDPJQWYGJJBYLF-UHFFFAOYSA-J hafnium tetrachloride Chemical compound Cl[Hf](Cl)(Cl)Cl PDPJQWYGJJBYLF-UHFFFAOYSA-J 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IUBCUJZHRZSKDG-UHFFFAOYSA-N C(C)N(C)[Hf] Chemical compound C(C)N(C)[Hf] IUBCUJZHRZSKDG-UHFFFAOYSA-N 0.000 description 2
- ZUGLFFHWVUUORL-UHFFFAOYSA-M CCN(C)[Hf+](N(C)CC)N(C)CC.[Cl-] Chemical compound CCN(C)[Hf+](N(C)CC)N(C)CC.[Cl-] ZUGLFFHWVUUORL-UHFFFAOYSA-M 0.000 description 2
- WDPRLGANSFXSFK-UHFFFAOYSA-N CCN(C)[Hf](N(C)CC)(N(CC(C)C)CC(C)C)N(CC(C)C)CC(C)C Chemical compound CCN(C)[Hf](N(C)CC)(N(CC(C)C)CC(C)C)N(CC(C)C)CC(C)C WDPRLGANSFXSFK-UHFFFAOYSA-N 0.000 description 2
- ZEPLKZPCPOSCHJ-UHFFFAOYSA-N CCN(C)[Hf](N(C)CC)(N(CC)C(C)C)N(CC)C(C)C Chemical compound CCN(C)[Hf](N(C)CC)(N(CC)C(C)C)N(CC)C(C)C ZEPLKZPCPOSCHJ-UHFFFAOYSA-N 0.000 description 2
- WZJFGRYNDUUFHV-UHFFFAOYSA-N CN(CC)[Hf](N(C)CC)N(C)CC Chemical compound CN(CC)[Hf](N(C)CC)N(C)CC WZJFGRYNDUUFHV-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- QCLXDOAJVSPZSK-UHFFFAOYSA-L [Cl-].[Cl-].C(C)N(C)[Hf+2]N(CC)C Chemical compound [Cl-].[Cl-].C(C)N(C)[Hf+2]N(CC)C QCLXDOAJVSPZSK-UHFFFAOYSA-L 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- NPEOKFBCHNGLJD-UHFFFAOYSA-N ethyl(methyl)azanide;hafnium(4+) Chemical compound [Hf+4].CC[N-]C.CC[N-]C.CC[N-]C.CC[N-]C NPEOKFBCHNGLJD-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000005211 surface analysis Methods 0.000 description 2
- WHRNULOCNSKMGB-UHFFFAOYSA-N tetrahydrofuran thf Chemical compound C1CCOC1.C1CCOC1 WHRNULOCNSKMGB-UHFFFAOYSA-N 0.000 description 2
- 238000007736 thin film deposition technique Methods 0.000 description 2
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 1
- ZWXQPERWRDHCMZ-UHFFFAOYSA-N 2-methyl-n-propan-2-ylpropan-2-amine Chemical compound CC(C)NC(C)(C)C ZWXQPERWRDHCMZ-UHFFFAOYSA-N 0.000 description 1
- YCLZAWVMMSQWJV-UHFFFAOYSA-N CCC(C)N(C(C)CC)[Hf](N(C)CC)(N(C)CC)N(C)CC Chemical compound CCC(C)N(C(C)CC)[Hf](N(C)CC)(N(C)CC)N(C)CC YCLZAWVMMSQWJV-UHFFFAOYSA-N 0.000 description 1
- BKIFMYUCNVIHST-UHFFFAOYSA-K CCN(C)[Hf+3].[Cl-].[Cl-].[Cl-] Chemical compound CCN(C)[Hf+3].[Cl-].[Cl-].[Cl-] BKIFMYUCNVIHST-UHFFFAOYSA-K 0.000 description 1
- JIIRDPLWVIYBFJ-UHFFFAOYSA-N CCN(C)[Hf](N(C)CC)(N(C)CC)N(C(C)C)C(C)C Chemical compound CCN(C)[Hf](N(C)CC)(N(C)CC)N(C(C)C)C(C)C JIIRDPLWVIYBFJ-UHFFFAOYSA-N 0.000 description 1
- FVOJEGCFTZCUQZ-UHFFFAOYSA-N CCN(C)[Hf](N(C)CC)N(CC)C(C)C Chemical compound CCN(C)[Hf](N(C)CC)N(CC)C(C)C FVOJEGCFTZCUQZ-UHFFFAOYSA-N 0.000 description 1
- 241000252506 Characiformes Species 0.000 description 1
- 101150065749 Churc1 gene Proteins 0.000 description 1
- 229910003855 HfAlO Inorganic materials 0.000 description 1
- 229910004143 HfON Inorganic materials 0.000 description 1
- 229910004129 HfSiO Inorganic materials 0.000 description 1
- 102100038239 Protein Churchill Human genes 0.000 description 1
- LSHFIWNMHGCYRS-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[OH4+2] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[OH4+2] LSHFIWNMHGCYRS-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000000277 atomic layer chemical vapour deposition Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010438 heat treatment Methods 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
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- KNFPLMFTXFVFPA-UHFFFAOYSA-N lithium;bis(2-methylpropyl)azanide Chemical compound CC(C)CN([Li])CC(C)C KNFPLMFTXFVFPA-UHFFFAOYSA-N 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- XQOIBQBPAXOVGP-UHFFFAOYSA-N n-ethyl-2-methylpropan-2-amine Chemical compound CCNC(C)(C)C XQOIBQBPAXOVGP-UHFFFAOYSA-N 0.000 description 1
- RIVIDPPYRINTTH-UHFFFAOYSA-N n-ethylpropan-2-amine Chemical compound CCNC(C)C RIVIDPPYRINTTH-UHFFFAOYSA-N 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
- C23C16/405—Oxides of refractory metals or yttrium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic Table without C-Metal linkages
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
- C23C16/18—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metallo-organic compounds
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—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
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—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
- C23C16/308—Oxynitrides
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- 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
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- 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
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- 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
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- 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
- C23C16/45531—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 specially adapted for making ternary or higher compositions
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- 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
Definitions
- the present application relates to a hafnium precursor compound, a precursor composition for forming a hafnium-containing film including the hafnium precursor compound, and a method of forming a hafnium-containing film using the precursor composition.
- the hafnium-containing oxide thin film is one of the thin films essential for driving microelectronic devices such as semiconductors (DRAM, Flash Memory, ReRAM, PCRAM, etc.) as well as non-semiconductors (logic).
- microelectronic devices such as semiconductors (DRAM, Flash Memory, ReRAM, PCRAM, etc.) as well as non-semiconductors (logic).
- logic non-semiconductors
- OLEDs organic light emitting diodes
- a gate insulating film, a capacitor high dielectric film, and a hafnium-containing oxide thin film are used in the display field.
- a hafnium oxide film is being evaluated as a high-k film of a storage capacitor in an organic light emitting diode.
- hafnium-containing precursors suitable for process temperatures for various application fields are required, and an atomic layer deposition method that has excellent thermal stability and can secure a wide process window to overcome step coverage due to a high aspect ratio
- ALD atomic layer eeposition
- the hafnium-containing oxide thin film is formed using the atomic layer deposition method, it is expected that the thickness uniformity and physical properties of the thin film can be improved, and the characteristics of semiconductor devices can be improved over a wide process temperature range.
- a high-k material is required due to high integration and scaling down of the device, so the development of a new hafnium precursor is essential.
- atomic layer deposition a deposition method capable of forming a uniform thin film with self-limiting characteristics, should be used even in order to secure the process temperature, dielectric properties and diffusion barrier properties that may occur during the process, Appropriate hafnium precursors should be used. Therefore, many studies are being conducted on the development of a precursor compound for forming a hafnium-containing oxide thin film capable of obtaining a film having desired properties by atomic layer deposition.
- the present application provides a hafnium precursor compound, a precursor composition for forming a hafnium-containing film including the hafnium precursor compound, and a method of forming a hafnium-containing film using the precursor composition.
- a first aspect of the present application provides a hafnium precursor compound represented by the following formula (1):
- x 1, 2 or 3
- R 1 , R 2 , R 3 and R 4 are each independently a linear or branched C 1 -C 5 alkyl group
- -NR 1 R 2 and -NR 3 R 4 are different from each other.
- a second aspect of the present application provides a precursor composition for forming a hafnium-containing film, comprising the hafnium precursor compound according to the first aspect.
- a third aspect of the present application provides a method for forming a hafnium-containing film, comprising forming a hafnium-containing film by using the precursor composition for film formation including the hafnium precursor compound according to the first aspect.
- a hafnium-containing film may be formed using a hafnium precursor compound according to embodiments of the present disclosure.
- a hafnium-containing film may be formed at a relatively low temperature using a hafnium precursor compound according to embodiments of the present disclosure.
- a hafnium-containing film of good quality may be formed even at a relatively low temperature of about 200° C. to about 300° C. using the hafnium precursor compound according to embodiments of the present disclosure.
- the hafnium precursor compound according to the embodiments of the present disclosure may be used as a precursor of an atomic layer deposition method or a chemical vapor deposition method due to the high vapor pressure, low density, and high thermal stability of the compound.
- the hafnium precursor compound according to the embodiments of the present disclosure is used to form a hafnium-containing film, particularly, a hafnium oxide film
- the content of carbon included in the formed film may be reduced.
- a hafnium-containing film, particularly, a hafnium oxide film is formed by an atomic layer deposition method using ozone using the hafnium precursor compound according to the embodiments of the present application, the content of carbon included in the formed film may be reduced.
- a thin film deposition method using a hafnium precursor compound according to embodiments of the present disclosure is to deposit a hafnium-containing oxide thin film or a nitride thin film on a substrate by an atomic layer deposition method using a hafnium precursor compound.
- a hafnium-containing metal film or thin film As such, using the atomic layer deposition method, a hafnium-containing metal film or thin film, a hafnium-containing oxide film or thin film, a hafnium-containing nitride film or thin film, a hafnium-containing carbide film or thin film, a hafnium-containing oxynitride film or thin film, and If a hafnium-containing carbonitride film or thin film is deposited, the process temperature during deposition can be lowered and the thickness and composition of the thin film can be precisely controlled, so that a thin film having excellent coverage can be deposited even on a substrate with a complex shape. It is possible to improve the thickness uniformity and physical properties of the thin film.
- the thin film deposition method using the hafnium precursor compound according to the embodiments of the present application may be used for manufacturing a memory device, a logic device, a display device, or an OLED device.
- Figures 2a and 2b the HfO 2 using the hafnium precursor prepared by the method of Examples 1, 2, 3, and 5 of the Examples of the present application It shows the XPS surface analysis results of the thin film.
- CpHf(NMe 2 ) 3 and the HfO 2 thin film using the hafnium precursor prepared by the method of Examples 2, 3, and 6 of the Examples of the present application shows the SIMS component analysis results.
- step to or “step for” does not mean “step for”.
- alkyl refers to a linear or branched alkyl group having 1 to 12 carbon atoms, 1 to 10 carbon atoms, 1 to 8 carbon atoms, or 1 to 5 carbon atoms. and all possible isomers thereof.
- the alkyl or alkyl group is a methyl group (Me), an ethyl group (Et), an n-propyl group ( n Pr), an iso-propyl group ( i Pr), an n-butyl group ( n Bu), an iso-butyl group ( i Bu), tert-butyl group (tert-Bu, t Bu), sec-butyl group (sec-Bu, sec Bu), n-pentyl group ( n Pe), iso-pentyl group ( iso Pe), sec -pentyl group ( sec Pe), tert-pentyl group ( t Pe), neo-pentyl group ( neo Pe), 3-pentyl group, n-hexyl group, iso-hexyl group, heptyl group, 4,4-dimethylphen a tyl group, an octyl group, a 2,2,4-trimethylpentyl group
- ALD window may mean a temperature range suitable for an ALD process to occur, which means that ALD reacts according to the temperature of the process, and the physical properties of the formed or deposited film This is an important factor in the ALD process because it is different.
- a first aspect of the present application provides a hafnium precursor compound represented by the following formula (1):
- x 1, 2 or 3
- R 1 , R 2 , R 3 and R 4 are each independently a linear or branched C 1 -C 5 alkyl group, provided that -NR 1 R 2 and -NR 3 R 4 are different from each other.
- R 1 and R 2 are each independently, a methyl group, an ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec- butyl group, tert-butyl group, n-pentyl group, iso-pentyl group, sec-pentyl group, tert-pentyl group, neo-pentyl group or 3-pentyl group
- R 3 and R 4 are each independently, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, iso-pentyl group, sec-pentyl group, tert It may be a -pentyl group, a neo-pent
- the -NR 1 R 2 Is -NMeEt
- the -NR 3 R 4 is, -N ( iso Pr) 2, -NEt ( iso Pr), -N ( iso Pr) ( tert Bu) , NEt ( tert Bu), -N ( sec Bu) 2 or -N( iso Bu) 2 It may be, but is not limited thereto.
- the hafnium precursor compound may be selected from the following compounds, but is not limited thereto:
- a second aspect of the present application provides a precursor composition for forming a hafnium-containing film, comprising the hafnium precursor compound according to the first aspect.
- the hafnium precursor compound may include one or more selected from the following compounds, but is not limited thereto:
- the film is a hafnium-containing metal film or thin film, hafnium-containing oxide film or thin film, hafnium-containing nitride film or thin film, hafnium-containing carbide film or thin film, hafnium-containing oxynitride film or thin film , and hafnium-containing carbonitride film or thin film may be at least one selected from, but is not limited thereto.
- the hafnium-containing film may be a hafnium oxide film.
- it may further include one or more nitrogen sources selected from ammonia, nitrogen, hydrazine, and dimethyl hydrazine, but is not limited thereto.
- a third aspect of the present application provides a method for forming a hafnium-containing film, comprising forming a hafnium-containing film by using the precursor composition for film formation including the hafnium precursor compound according to the first aspect.
- the hafnium precursor compound included in the precursor composition for film formation may include one or more selected from the following compounds, but is not limited thereto:
- the hafnium-containing film may be deposited by a chemical vapor deposition method or an atomic layer deposition method, but is not limited thereto.
- the chemical vapor deposition method or the atomic layer deposition method may be performed using a deposition apparatus, deposition conditions, and additional reaction gas known in the art.
- a hafnium-containing oxide film or a composite metal hafnium-containing oxide film (HfSiO x , ZrHfO x , TiHfO x , HfAlO x , ZrAlHfO x , TiAlHfO x , ZrHfSiO x , ZrHfAlSiO x , HfC , HfCO , or HfON , etc.) It is preferable to use at least one from N 2 O Plasma), oxygen nitrate (N 2 O 2 ), hydrogen peroxide (H 2 O 2 ), sulfuric acid (H 2 SO 4 ) and ozone (O 3 ).
- the hafnium precursor compound with argon (Ar) or nitrogen (N 2 ) gas, use thermal energy or plasma, or apply a bias on the substrate to vaporize the hafnium precursor compound.
- Ar argon
- N 2 nitrogen
- the hafnium-containing film may be formed in a temperature range of about 100 °C to about 500 °C, but is not limited thereto.
- the hafnium-containing membrane is about 100 °C to about 500 °C, about 100 °C to about 450 °C, about 100 °C to about 400 °C, about 100 °C to about 350 °C, about 100 °C to about 300 °C, about 100 °C to about 250 °C, about 100 °C to about 200 °C, about 100 °C to about 150 °C, about 150 °C to about 500 °C, about 150 °C to about 450 °C, about 150 °C to about 400 °C, about 150 °C to about 350 °C, about 150 °C to about 300 °C, about 150 °C to about 250 °C, about 150 °C to about 200 °C, about 200 °C to about 500 °C, about 200 °C, about 200 °C, about
- the hafnium-containing membrane is from about 200 °C to about 300 °C, from about 200 °C to about 280 °C, from about 200 °C to about 260 °C, from about 220 °C to about 280 °C, or from about 240 °C to about 240 °C It may be formed in a temperature range of about 280 °C.
- the method for forming a hafnium-containing film includes receiving a substrate in a reaction chamber, and then transferring the hafnium precursor compound onto the substrate using a transport gas or a diluent gas, and then at about 100° C. to about 500° C., Alternatively, it is desirable to deposit the hafnium-containing film at a deposition temperature ranging from about 200° C. to about 300° C.
- the deposition temperature is about 100°C to about 500°C, or about 200°C to about 300°C
- the process temperature applicable to memory devices, logic devices, and display devices is wide, so it is highly applicable to various fields and has a wide temperature range.
- a hafnium precursor compound usable in the range is required, it is preferred that the deposition be carried out in the range of from about 100°C to about 500°C, or from about 200°C to about 300°C.
- one or more mixed gases selected from argon (Ar), nitrogen (N 2 ), helium (He) or hydrogen (H 2 ) as the transport gas or diluent gas.
- the hafnium-containing film may be formed on one or more substrates selected from conventional hafnium semiconductor wafers, compound semiconductor wafers, and plastic substrates (PI, PET, PES, and PEN). , but is not limited thereto.
- a substrate having holes or grooves may be used, and a porous substrate having a large surface area may be used, but the present invention is not limited thereto.
- the hafnium-containing film may be formed on all or part of a substrate simultaneously or sequentially on a substrate to which two or more different types of substrates are in contact with or connected to each other, but is not limited thereto.
- the hafnium-containing film may be formed in a thickness range of about 1 nm to about 500 nm, but is not limited thereto.
- the hafnium-containing film is from about 1 nm to about 500 nm, from about 1 nm to about 400 nm, from about 1 nm to about 300 nm, from about 1 nm to about 200 nm, from about 1 nm to about 100 nm, from about 1 nm to about 50 nm, about 1 nm to about 40 nm, about 1 nm to about 30 nm, about 1 nm to about 20 nm, about 1 nm to about 10 nm, about 10 nm to about 500 nm, about 10 nm to about 400 nm , about 10 nm to about 300 nm, about 10 nm to about 200 nm, about 10 nm to about 100 nm, about 10 nm to about 50 nm, about 10 nm to about 300
- the hafnium-containing film may be formed on a substrate including irregularities having an aspect ratio of about 1 or more and a width of about 1 ⁇ m or less, but may not be limited thereto.
- the aspect ratio is about 1 or more, about 5 or more, about 10 or more, about 20 or more, about 30 or more, about 40 or more, about 1 to about 50, about 1 to about 40, about 1 to about 30, about 1 to about 20, about 1 to about 10, about 10 to about 50, about 10 to about 40, about 10 to about 30, about 10 to about 20, about 20 to about 50, about 20 to about 40, about 20 to It may be about 30, about 30 to about 50, about 30 to about 40, or about 40 to about 50, but may not be limited thereto.
- the width is about 1 ⁇ m or less, about 900 nm or less, about 800 nm or less, about 700 nm or less, about 600 nm or less, about 500 nm or less, about 400 nm or less, about 300 nm or less, about 200 nm or less, about 100 nm or less, about 10 nm to about 1 ⁇ m, about 10 nm to about 900 nm, about 10 nm to about 800 nm, about 10 nm to about 700 nm, about 10 nm to about 600 nm, about 10 nm to about 500 nm, about 10 nm to about 400 nm, about 10 nm to about 300 nm, about 10 nm to about 200 nm, about 10 nm to about 100 nm, about 10 nm to about 90 nm, about 10 nm to about 80 nm, about 10 nm to about 70 nm, about 10 nm to about 60 .
- the hafnium precursor compound of the present application included in the precursor composition for film formation is used as a precursor of atomic layer deposition or chemical vapor deposition due to high vapor pressure, low density, and high thermal stability.
- hafnium-containing metal films or thin films hafnium-containing oxide films or thin films, hafnium-containing nitride films or thin films, hafnium-containing carbide films or thin films, hafnium-containing oxynitride films or thin films, and hafnium-containing oxynitride films or thin films. It has an excellent effect of uniformly forming a carbonitride-containing film or thin film.
- Example 1 Preparation of (diisopropylamino)tris(ethyl(methyl)amino)hafnium: [ ⁇ ((CH 3 ) 2 HC) 2 N ⁇ Hf ⁇ N(C 2 H 5 )(CH 3 ) ⁇ 3 ]
- HfCl 4 hafnium (IV) chloride
- lithium diisopropylamide lithium diisopropylamide
- LiN( i Pr) 2 LiN( i Pr) 2
- the temperature was gradually raised to room temperature, and then using a reflux condenser for 17 hours. during reflux reaction.
- the salt generated during the reaction is removed through filtration, and the solvent and volatile side reactants are removed by distillation under reduced pressure.
- Example 2 Preparation of (disecbutylamino)tris(ethyl(methyl)amino)hafnium : [ ⁇ ((C 2 H 5 )(CH 3 )HC) 2 N ⁇ Hf ⁇ N(C 2 H 5 )(CH 3 ) ⁇ 3 ]
- (disecbutylamino)tris(ethyl) which is a colorless liquid compound represented by the following Chemical Formula 3 in the same manner as in Example 1, except that disec butylamine was used instead of diisopropylamine (methyl)amino)hafnium [(disecbutylamino)tris[(ethyl)(methyl)amino)hafnium; ⁇ ( sec Bu) 2 N ⁇ Hf ⁇ N(Et)(Me) ⁇ 3 ] 174.88 g (yield: 58%) was obtained.
- Example 3 (Tibutyl(ethyl)amino)tris(ethyl(methyl)amino)hafnium preparation: [ ⁇ ((CH 3 ) 3 C)(C 2 H 5 )N ⁇ Hf ⁇ N(C 2 H 5 ) (CH 3 ) ⁇ 3 ]
- Example 4 (Tibutyl(isopropyl)amino)tris(ethyl(methyl)amino)hafnium preparation: [ ⁇ ((CH 3 ) 3 C)((CH 3 ) 2 HC)N ⁇ Hf ⁇ N(C 2 ) H 5 )(CH 3 ) ⁇ 3 ]
- HfCl 4 hafnium (IV) chloride
- Example 6 Bis(ethyl(isopropyl)amino)bis(ethyl(methyl)amino)hafnium preparation: [ ⁇ (C 2 H 5 )((CH 3 ) 2 HC)N ⁇ 2 Hf ⁇ N(C 2 H) 5 )(CH 3 ) ⁇ 2 ]
- An atomic layer deposition (ALD) process was performed using the hafnium precursor compounds prepared by the methods of Examples 1, 2, 3, 5, and 6 above.
- As the reaction gas O 3 as an oxygen source was used.
- the silicon wafer was immersed in a piranha solution in which sulfuric acid (H 2 SO 4 ) and hydrogen peroxide (H 2 O 2 ) were mixed in a ratio of 4:1 for 10 minutes and then immersed in a dilute HF aqueous solution for about 2 minutes. After forming a pure silicon surface, a hafnium oxide thin film was prepared by atomic layer deposition (ALD).
- the ALD cycle was fixed 100 times, and the temperature of the substrate was heated from 200°C to 300°C at 20°C intervals for deposition.
- Hafnium precursor compounds were used by heating to 100 °C, 115 °C, 100 °C, 135 °C, and 105 °C, respectively, in a container made of stainless steel.
- the process pressure of the reactor was 1 torr, and argon (Ar) gas having a flow rate of 300 sccm was used as a carrier gas of the precursor compound and vaporized.
- the ALD cycle was each vaporized precursor supply 5 seconds, precursor purge (purge) 10 seconds, O 3 exposure time 5 seconds, O 3 purge (purge) 10 seconds.
- the deposition results are shown in FIG. 1 .
- the ALD window can be confirmed from the deposition results of the hafnium precursors prepared by the methods of Examples 1, 3, and 5 among the prepared hafnium precursor compounds.
- the characteristics of the ALD window at such a relatively low temperature, when the process is performed at a low temperature, can suppress oxidation of the lower electrode to improve the electrical characteristics, and the method of Examples 1, 2, 3, 5, and 6
- the hafnium precursor compounds prepared by the present invention are excellent precursors that can satisfy the above properties, and can be used in various fields of semiconductor processing.
- FIG. 3 CpHf(NMe 2 ) 3 and the hafnium precursor prepared by the methods of Examples 2, 3, and 6, which are currently commercially available, shows the SIMS component analysis results of the HfO 2 thin film.
- SIMS analysis was performed on HfO 2 thin films deposited at 240 °C.
- the element to be compared is carbon, and as a result of the analysis, the carbon content of the HfO 2 thin film using the hafnium precursor prepared by the methods of Examples 2, 3, and 6 is higher than the carbon content of the HfO 2 thin film using CpHf(NMe 2 ) 3 It was lower.
- Examples 2, 3, and 6, are 31937, 28169, 23494, and 27388, respectively, and the reduction rate Compared to the hafnium precursors prepared by the methods of Examples 2, 3, and 6, CpHf(NMe 2 ) 3 Compared to CpHf(NMe 2 ) 3, the reduction rate of CpHf(NMe 2 ) 3 is the highest with 11.8%, 26.4%, and 14.2% reduction, respectively, and , Example 3 had the lowest reduction rate (Example 3 ⁇ Example 6 ⁇ Example 2 ⁇ CpHf(NMe 2 ) 3 ).
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Abstract
Description
Claims (14)
- 하기 화학식 1로서 표시되는, 하프늄 전구체 화합물:[화학식 1](R1R2N)xHf(NR3R4)4-x;상기 화학식 1에서,x는 1, 2 또는 3이고,R1, R2, R3 및 R4는, 각각 독립적으로, 선형 또는 분지형의 C1-C5 알킬기이며,단, -NR1R2 및 -NR3R4는 서로 다른 것임.
- 제 1 항에 있어서,상기 화학식 1에서,R1 및 R2는, 각각 독립적으로, 메틸기, 에틸기, n-프로필기, iso-프로필기, n-부틸기, iso-부틸기, sec-부틸기, tert-부틸기, n-펜틸기, iso-펜틸기, sec-펜틸기, tert-펜틸기, neo-펜틸기 또는 3-펜틸기이고,R3 및 R4는, 각각 독립적으로, 메틸기, 에틸기, n-프로필기, iso-프로필기, n-부틸기, iso-부틸기, sec-부틸기, tert-부틸기, n-펜틸기, iso-펜틸기, sec-펜틸기, tert-펜틸기, neo-펜틸기 또는 3-펜틸기인, 하프늄 전구체 화합물.
- 제 1 항에 있어서,상기 -NR1R2는, -NMeEt 이고,상기 -NR3R4는, -N(isoPr)2, -NEt(isoPr), -N(isoPr)(tertBu), NEt(tertBu), -N(secBu)2 또는 -N (isoBu)2인 것인,하프늄 전구체 화합물.
- 제 1 항 내지 제 4 항 중 어느 한 항에 따른 하프늄 전구체 화합물을 포함하는, 하프늄-함유 막 형성용 전구체 조성물.
- 제 5 항에 있어서,상기 막은 하프늄 금속 막, 하프늄-함유 산화 막, 하프늄-함유 질화 막, 하프늄-함유 탄화 막, 하프늄-함유 산질화 막, 및 하프늄-함유 탄질화 막에서 선택되는 하나 이상인 것인, 하프늄-함유 막 형성용 전구체 조성물.
- 제 5 항에 있어서,암모니아, 질소, 히드라진, 및 디메틸 히드라진에서 선택되는 하나 이상의 질소원을 추가 포함하는, 하프늄-함유 막 형성용 전구체 조성물.
- 제 5 항에 있어서,수증기, 산소, 및 오존에서 선택되는 하나 이상의 산소원을 추가 포함하는, 하프늄-함유 막 형성용 전구체 조성물.
- 제 1 항 내지 제 4 항 중 어느 한 항에 따른 하프늄 전구체 화합물을 포함하는 막 형성용 전구체 조성물을 이용하여 하프늄-함유 막을 형성하는 것을 포함하는, 하프늄-함유 막 형성 방법.
- 제 10 항에 있어서,상기 하프늄-함유 막은 화학기상 증착법 또는 원자층 증착법에 의해 증착되는 것인, 하프늄-함유 막 형성 방법.
- 제 10 항에 있어서,상기 하프늄-함유 막은 100℃ 내지 500℃의 온도 범위에서 형성되는 것인, 하프늄-함유 막 형성 방법.
- 제 10 항에 있어서,상기 하프늄-함유 막은 1 nm 내지 500 nm의 두께 범위에서 형성되는 것인, 하프늄-함유 막 형성 방법.
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