WO2024117809A1 - Precursor for forming yttrium- or scandium-containing thin film, method for forming yttrium- or scandium-containing thin film using same, and semiconductor device comprising the yttrium- or scandium-containing thin film - Google Patents
Precursor for forming yttrium- or scandium-containing thin film, method for forming yttrium- or scandium-containing thin film using same, and semiconductor device comprising the yttrium- or scandium-containing thin film Download PDFInfo
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- WO2024117809A1 WO2024117809A1 PCT/KR2023/019540 KR2023019540W WO2024117809A1 WO 2024117809 A1 WO2024117809 A1 WO 2024117809A1 KR 2023019540 W KR2023019540 W KR 2023019540W WO 2024117809 A1 WO2024117809 A1 WO 2024117809A1
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- 239000010409 thin film Substances 0.000 title claims abstract description 105
- 239000002243 precursor Substances 0.000 title claims abstract description 75
- 238000000034 method Methods 0.000 title claims abstract description 71
- 229910052706 scandium Inorganic materials 0.000 title claims abstract description 21
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 239000004065 semiconductor Substances 0.000 title claims abstract description 11
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 23
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims abstract description 23
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 239000000758 substrate Substances 0.000 claims description 21
- 125000006165 cyclic alkyl group Chemical group 0.000 claims description 15
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 15
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 12
- 238000005229 chemical vapour deposition Methods 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 9
- 238000000231 atomic layer deposition Methods 0.000 claims description 9
- 238000000151 deposition Methods 0.000 claims description 9
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 6
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 claims description 6
- 230000008021 deposition Effects 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 6
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims description 6
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 6
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- UOCJDOLVGGIYIQ-PBFPGSCMSA-N cefatrizine Chemical group S([C@@H]1[C@@H](C(N1C=1C(O)=O)=O)NC(=O)[C@H](N)C=2C=CC(O)=CC=2)CC=1CSC=1C=NNN=1 UOCJDOLVGGIYIQ-PBFPGSCMSA-N 0.000 claims description 3
- ZOCHARZZJNPSEU-UHFFFAOYSA-N diboron Chemical compound B#B ZOCHARZZJNPSEU-UHFFFAOYSA-N 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 239000001272 nitrous oxide Substances 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 229910000077 silane Inorganic materials 0.000 claims description 3
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 3
- 230000008016 vaporization Effects 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000126 substance Substances 0.000 abstract description 12
- 239000003446 ligand Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 abstract description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 abstract description 2
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- -1 pentadienyl Chemical group 0.000 description 19
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 18
- 230000015572 biosynthetic process Effects 0.000 description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 16
- 229910052751 metal Inorganic materials 0.000 description 15
- 239000002184 metal Substances 0.000 description 15
- 238000003786 synthesis reaction Methods 0.000 description 14
- 239000002904 solvent Substances 0.000 description 13
- 238000005481 NMR spectroscopy Methods 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 8
- OBOSXEWFRARQPU-UHFFFAOYSA-N 2-n,2-n-dimethylpyridine-2,5-diamine Chemical compound CN(C)C1=CC=C(N)C=N1 OBOSXEWFRARQPU-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000000113 differential scanning calorimetry Methods 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 238000002411 thermogravimetry Methods 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- BDNKZNFMNDZQMI-UHFFFAOYSA-N 1,3-diisopropylcarbodiimide Chemical compound CC(C)N=C=NC(C)C BDNKZNFMNDZQMI-UHFFFAOYSA-N 0.000 description 1
- IQSUNBLELDRPEY-UHFFFAOYSA-N 1-ethylcyclopenta-1,3-diene Chemical compound CCC1=CC=CC1 IQSUNBLELDRPEY-UHFFFAOYSA-N 0.000 description 1
- VKWMOOFWZGJOQO-UHFFFAOYSA-N 5,5-diethylcyclopenta-1,3-diene Chemical compound CCC1(CC)C=CC=C1 VKWMOOFWZGJOQO-UHFFFAOYSA-N 0.000 description 1
- 241000349731 Afzelia bipindensis Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052767 actinium Inorganic materials 0.000 description 1
- QQINRWTZWGJFDB-UHFFFAOYSA-N actinium atom Chemical compound [Ac] QQINRWTZWGJFDB-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
- 239000006227 byproduct Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- BGRWYRAHAFMIBJ-UHFFFAOYSA-N diisopropylcarbodiimide Natural products CC(C)NC(=O)NC(C)C BGRWYRAHAFMIBJ-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- NFWSQSCIDYBUOU-UHFFFAOYSA-N methylcyclopentadiene Chemical compound CC1=CC=CC1 NFWSQSCIDYBUOU-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- DAZXVJBJRMWXJP-UHFFFAOYSA-N n,n-dimethylethylamine Chemical compound CCN(C)C DAZXVJBJRMWXJP-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000009832 plasma treatment Methods 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
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
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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
- C23C16/06—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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- C07F17/00—Metallocenes
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- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
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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
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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
- C23C16/308—Oxynitrides
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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
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- 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
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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
- C23C16/405—Oxides of refractory metals or yttrium
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- 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
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- 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
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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
- C23C16/44—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
- C23C16/50—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 using electric discharges
Definitions
- the present invention relates to a precursor for forming a thin film containing yttrium (Y) or scandium (Sc), a method of forming a thin film containing yttrium or scandium using the same, and a semiconductor device including the thin film containing yttrium or scandium, and more specifically, to an asymmetric cycle.
- a precursor for forming thin films containing yttrium or scandium which provides a precursor with high heat resistance and high volatility through a chemical structure containing a pentadienyl ligand and an asymmetric amidinate ligand, and can form a high-quality thin film through this, and a thin film using the same It relates to a forming method and a semiconductor device including the thin film.
- the present invention was conceived in consideration of the above prior arts, and its purpose is to provide a novel yttrium- or scandium-containing thin film-forming precursor that can exhibit chemical properties suitable as a thin film-forming precursor.
- the purpose is to provide a precursor for forming a thin film containing yttrium or scandium, which exhibits chemical properties of high heat resistance and high volatility, and is in a liquid state at room temperature, a solid state with a low melting point, or a solid state with high solubility in a solvent. do.
- the purpose is to provide a method of forming a thin film using the precursor.
- the object is to provide a semiconductor device including the thin film.
- the precursor for forming a thin film of the present invention to solve the above problems is characterized by containing a compound represented by the following formula (1).
- M is yttrium (Y) or scandium (Sc), and R 1 to R 8 are each independently a hydrogen atom, or a C 1 -C 6 straight-chain, branched or cyclic alkyl group, alkenyl group, alkoxy group, or amine group. Or it is a silyl group.
- R 6 and R 8 may be different C 1 -C 6 straight-chain, branched, or cyclic alkyl groups.
- R 1 to R 5 may be different C 1 -C 6 straight-chain, branched, or cyclic alkyl groups.
- R 6 and R 8 are different C 1 -C 6 straight-chain, branched or cyclic alkyl groups, or at least two of R 1 to R 5 are different C 1 -C 6 alkyl groups. It may be a straight-chain, branched, or cyclic alkyl group.
- R 1 to R 5 may be an ethyl group (Et) or a methyl group (Me).
- R 6 and R 8 may be a C 1 -C 6 branched alkyl group.
- any one or more of R 6 and R 8 is a t-butyl group (t-Bu), s-butyl group (sec-Bu), isobutyl group (i-Bu), or isopropyl group. (iPr), or t-amyl group.
- one of R 6 and R 8 may be a t-butyl group and the other may be an isopropyl group.
- R 7 is an ethyl group (Et), n-propyl group (n-Pr), n-butyl group (n-Bu), isopropyl group (i-Pr), s-butyl group (sec- Bu) or isobutyl group (i-Bu).
- the thin film forming method of the present invention is characterized by including a process of forming a thin film on a substrate using the thin film forming precursor.
- the process of forming a thin film on the substrate may include a process of forming a precursor thin film by depositing the thin film forming precursor on the surface of the substrate, and a process of reacting the precursor thin film with a reactive gas.
- the reactive gases include nitrogen (N 2 ), ammonia (NH 3 ), hydrazine (N 2 H 4 ), nitrous oxide (N 2 O), oxygen (O 2 ), water vapor (H 2 O), and ozone (O). 3 ), one or more of hydrogen peroxide (H 2 O 2 ), silane, hydrogen (H 2 ), and diborane (B 2 H 6 ) can be used.
- the process of forming the precursor thin film may include vaporizing the thin film forming precursor and transferring it into the chamber.
- the deposition is a spin-on dielectric (SOD) process, a low temperature plasma (LTP) process, a chemical vapor deposition (CVD) process, and a plasma enhanced chemical vapor deposition (CVD) process.
- SOD spin-on dielectric
- LTP low temperature plasma
- CVD chemical vapor deposition
- CVD plasma enhanced chemical vapor deposition
- PECVD plasma enhanced chemical vapor deposition
- HDPCVD High Density Plasma -Chemical Vapor Deposition
- ALD Atomic Layer Deposition
- PEALD Plasma-Enhanced Atomic Layer Deposition
- the process of forming a thin film on the substrate may include supplying the thin film forming precursor to the substrate and applying plasma to form the thin film.
- the semiconductor device of the present invention is characterized by including a thin film manufactured by the above thin film forming method.
- the precursor for forming a yttrium- or scandium-containing thin film according to the present invention contains an asymmetric cyclopentadienyl and an asymmetric amidinate ligand, so the precursor compound has excellent structural stability and exhibits high volatility and high heat resistance characteristics, thereby forming a yttrium- or scandium-containing thin film. It shows an effect suitable for use in the forming process.
- a high-quality yttrium- or scandium-containing thin film can be formed using the thin film forming precursor, and a semiconductor device including a yttrium- or scandium-containing thin film manufactured by the thin film forming method can be provided.
- Figure 1 shows the 1 H NMR analysis results of bis(ethylcyclopentadienyl)(isopropyl-t-butyl-methylamidinato)yttrium.
- Figure 2 shows the TGA analysis results of bis(ethylcyclopentadienyl)(isopropyl-t-butyl-methylamidinato)yttrium.
- Figure 3 shows the DSC analysis results of bis(ethylcyclopentadienyl)(isopropyl-t-butyl-methylamidinato)yttrium.
- Figure 4 shows the 1 H NMR analysis results of bis(ethylcyclopentadienyl)(isopropyl-t-butyl-ethylamidinato)yttrium.
- Figure 5 shows the 1 H NMR analysis results of bis(diethylcyclopentadienyl)(isopropyl-t-butyl-methylamidinato)yttrium.
- Figure 6 shows the TGA analysis results of bis(diethylcyclopentadienyl)(isopropyl-t-butyl-methylamidinato)yttrium.
- Figure 7 shows the DSC analysis results of bis(diethylcyclopentadienyl)(isopropyl-t-butyl-methylamidinato)yttrium.
- Figure 8 shows the 1 H NMR analysis results of bis(ethylmethylcyclopentadienyl)(diisopropyl-methylamidinato)yttrium.
- the precursor for forming a thin film according to the present invention is for forming a thin film containing yttrium or scandium, and is characterized by containing a compound represented by the following formula (1).
- M is yttrium (Y) or scandium (Sc), and R 1 to R 8 are each independently a hydrogen atom, or a C 1 -C 6 straight-chain, branched or cyclic alkyl group, alkenyl group, alkoxy group, or amine group. Or it is a silyl group.
- the precursor for forming the thin film can form various types of compounds depending on the type of functional group.
- R 6 and R 8 may be different C 1 -C 6 straight-chain, branched, or cyclic alkyl groups.
- an asymmetric structure can be formed by different forms of R 6 and R 8 .
- R 1 to R 5 may be different C 1 -C 6 straight-chain, branched, or cyclic alkyl groups, thereby forming an asymmetric structure.
- R 6 and R 8 are different C 1 -C 6 straight-chain, branched or cyclic alkyl groups, or at least two of R 1 to R 5 are different C 1 -C 6 alkyl groups. It may be a straight-chain, branched, or cyclic alkyl group, which can increase the overall structural asymmetry of the compound.
- any one or more of R 1 to R 5 may be an ethyl group (Et) or a methyl group (Me), and one or more of R 6 and R 8 may be a C 1 -C 6 group. It may be a functional alkyl group, and one or more of R 6 and R 8 is a t-butyl group (t-Bu), s-butyl group (sec-Bu), isobutyl group (i-Bu), or isopropyl group. (iPr), or it may be a t-amyl group.
- R 6 and R 8 may be a t-butyl group and the other may be an isopropyl group
- R 7 may be an ethyl group (Et), an n-propyl group (n-Pr), or an n-butyl group (n- Bu), isopropyl group (i-Pr), s-butyl group (sec-Bu), or isobutyl group (i-Bu).
- This chemical structure was found to be suitable for forming a high-quality thin film because it has excellent structural stability and exhibits high volatility and high heat resistance properties.
- the thin film forming precursor of the present invention may additionally include a solvent for dissolving or diluting the precursor compound in consideration of the conditions and efficiency of the thin film forming process.
- the solvent may be any one of C 1 -C 16 saturated or unsaturated hydrocarbons, ketones, ethers, glymes, esters, tetrahydrofuran, tertiary amines, or mixtures thereof.
- Examples of the C 1 -C 16 saturated or unsaturated hydrocarbon include toluene and heptane, and examples of the tertiary amine include dimethylethylamine.
- the precursor compound for forming a thin film may be in a solid state at room temperature.
- the compound can be dissolved by including the solvent. That is, when the solvent is included, it is contained in a solvent and amount capable of dissolving the precursor compound, and is preferably contained in 1 to 99% by weight based on the total weight of the precursor for forming the thin film.
- a thin film is formed on a substrate using a precursor for forming a thin film containing or not containing the solvent.
- the process of forming a thin film on a substrate may include a process of forming a precursor thin film by depositing the thin film forming precursor on the surface of the substrate, and a process of reacting the precursor thin film with a reactive gas.
- the reactive gas is nitrogen (N 2 ), ammonia (NH 3 ), hydrazine (N 2 H 4 ), nitrous oxide (N 2 O), oxygen (O 2 ), water vapor (H 2 O), and ozone (O). 3 ), one or more of hydrogen peroxide (H 2 O 2 ), silane, hydrogen (H 2 ), and diborane (B 2 H 6 ) can be used.
- various types of thin films such as yttrium or scandium metal thin films, oxide, nitride, and oxynitride thin films, can be formed.
- the process of forming the precursor thin film may include a process of vaporizing the thin film forming precursor and transferring it into the chamber.
- a precursor containing a solvent may be used as described above. Additionally, if it exists in a liquid state at room temperature and can be vaporized, the thin film forming precursor can be transported into the chamber without a separate solvent.
- the deposition is a spin-on dielectric (SOD) process, a low temperature plasma (LTP) process, a chemical vapor deposition (CVD) process, and a plasma enhanced chemical vapor deposition (CVD) process.
- SOD spin-on dielectric
- LTP low temperature plasma
- CVD chemical vapor deposition
- CVD plasma enhanced chemical vapor deposition
- PECVD plasma enhanced chemical vapor deposition
- HDP-CVD High Density Plasma -Chemical Vapor Deposition
- ALD Atomic Layer Deposition
- PEALD Plasma-Enhanced Atomic Layer Deposition
- the process of forming a thin film on a substrate may include forming a thin film of a metal, oxide, nitride, oxynitride, etc. by supplying the thin film forming precursor to the substrate and applying plasma in the presence of a reactant.
- the process of forming the thin film can be performed under chamber pressure conditions of 1 to 1000 mTorr.
- the source power for forming plasma in the chamber is 500 to 9,000 W
- the bias power is 0 to 5,000 W. Additionally, the bias power may not be applied depending on the case.
- the process of forming a thin film on the substrate may be performed at a temperature range of 150 to 500°C.
- a second metal precursor may be introduced as needed to further improve the electrical properties, that is, capacitance or leakage current value, of the final formed metal film.
- the second metal precursor is silicon (Si), titanium (Ti), germanium (Ge), strontium (Sr), niobium (Nb), barium (Ba), hafnium (Hf), tantalum (Ta), and actinium (Ac).
- a metal precursor containing one or more metals (M") selected from atoms may be optionally further supplied.
- the second metal precursor may be an alkylamide-based compound or an alkoxy-based compound containing the metal.
- the second metal precursor is SiH(N(CH 3 ) 2 ) 3 , Si(N(C 2 H 5 ) 2 ) 4 , Si(N(C 2 H 5 )(CH 3 )) 4 , Si(N(CH 3 ) 2 ) 4 , Si(OC 4 H 9 ) 4 , Si(OC 2 H 5 ) 4 , Si(OCH 3 ) 4 , Si(OC(CH 3 ) 3 ) 4 , etc. can be used. You can.
- the supply of the second metal precursor may be carried out in the same manner as the supply method of the thin film formation precursor, and the second metal precursor may be supplied together with the precursor onto the thin film formation substrate, or the supply of the precursor may be completed. It may then be supplied sequentially.
- the precursor for forming the thin film and optionally the second metal precursor as described above are preferably maintained at a temperature of 50 to 250° C. before being supplied into the reaction chamber for contact with the substrate for forming the thin film, more preferably 100 to 200° C. It is recommended to maintain a temperature of °C.
- an inert gas such as argon (Ar), nitrogen (N 2 ), or helium (He) may be performed in the reactor. At this time, it is preferable that the inert gas is spread so that the pressure inside the reactor is 1 to 5 Torr.
- a heat treatment or light irradiation treatment process may be performed to provide heat energy for deposition of a thin film forming precursor, and may be performed according to a conventional method.
- the treatment process is preferably performed so that the temperature of the substrate in the reactor is 100 to 1,000°C, preferably 250 to 400°C. .
- argon is used in the reactor to help the reactant move onto the substrate, to maintain an appropriate pressure for deposition within the reactor, and to release impurities or by-products present in the reactor to the outside.
- a process of purging an inert gas such as (Ar), nitrogen (N 2 ), or helium (He) may be performed.
- a thin film can be formed by repeating the process one or more cycles.
- thin films manufactured by applying the thin film forming process can be used in various semiconductor devices.
- Li-( i Pr t BuMe-AMD) was prepared. The solution was stirred at -78°C for 30 minutes, then warmed to room temperature, and stirred for an additional 2 hours at room temperature. The prepared Li-( i Pr t BuMe-AMD) solution was slowly added dropwise to a flask containing (EtCp) 2 YCl at room temperature and stirred at room temperature for 12 hours.
- the light yellow solid sample was placed in an airtight container for DSC and maintained at 40°C for 10 minutes, and then a decomposition peak was observed at 439°C during DSC (Discovery 25, TA instrument) analysis measured at a temperature rise rate of 10°C/min. . These results are shown in Figure 3.
- the DSC analysis results showing the change in thermal energy according to temperature change are shown in Figure 3.
- Li-( i Pr t BuEt-AMD) was prepared. The solution was stirred at -78°C for 30 minutes, then warmed to room temperature, and stirred for an additional 2 hours at room temperature. The prepared Li-( i Pr t BuEt-AMD) solution was slowly added dropwise to a flask containing (EtCp) 2 YCl at room temperature and stirred at room temperature for 12 hours.
- Li-( i Pr t BuMe-AMD) was prepared. The solution was stirred at -78°C for 30 minutes, then warmed to room temperature, and stirred for an additional 2 hours at room temperature. The prepared Li-( i Pr t BuMe-AMD) solution was slowly added dropwise to a flask containing (Et 2 Cp) 2 YCl at room temperature and stirred at room temperature for 12 hours.
- the light yellow solid sample was placed in an airtight container for DSC and kept at 40°C for 10 minutes, and then a decomposition peak was observed above 400°C during DSC (Discovery 25, TA instrument) analysis measured at a temperature rise rate of 10°C/min. It has been done. These results are shown in Figure 7.
- the DSC analysis results showing the change in thermal energy according to the temperature change are shown in Figure 7.
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Abstract
The present invention relates to a precursor for forming an yttrium (Y)- or scandium (Sc)-containing thin film, the precursor comprising a compound represented by chemical formula 1, a method for forming an yttrium- or scandium-containing thin film using same, and a semiconductor device comprising the yttrium- or scandium-containing thin film. The precursor for forming a thin film has a chemical structure including an asymmetric cyclopentadienyl ligand and an asymmetric amidinate ligand, thus exhibiting high heat resistance and high volatility, and therefore, exhibits the effect of forming a high-quality thin film.
Description
본 발명은 이트륨(Y) 또는 스칸듐(Sc) 함유 박막 형성용 전구체, 이를 이용한 이트륨 또는 스칸듐 함유 박막 형성 방법 및 상기 이트륨 또는 스칸듐 함유 박막을 포함하는 반도체 소자에 관한 것으로서, 더욱 상세하게는, 비대칭 싸이클로펜타디에닐 리간드 및 비대칭 아미디네이트 리간드를 포함하는 화학구조를 통해 고내열성 및 고휘발성의 전구체를 제공하고, 이를 통해 고품질의 박막을 형성할 수 있는 이트륨 또는 스칸듐 함유 박막 형성용 전구체, 이를 이용한 박막 형성 방법 및 상기 박막을 포함하는 반도체 소자에 관한 것이다.The present invention relates to a precursor for forming a thin film containing yttrium (Y) or scandium (Sc), a method of forming a thin film containing yttrium or scandium using the same, and a semiconductor device including the thin film containing yttrium or scandium, and more specifically, to an asymmetric cycle. A precursor for forming thin films containing yttrium or scandium, which provides a precursor with high heat resistance and high volatility through a chemical structure containing a pentadienyl ligand and an asymmetric amidinate ligand, and can form a high-quality thin film through this, and a thin film using the same It relates to a forming method and a semiconductor device including the thin film.
반도체 소자의 선폭 미세화를 통한 집적도 향상으로 커패시터 구조 구현에 허용되는 공간이 선폭적으로 제한되면서, 기존 실리콘계 유전체로는 커패시터 구조 구현을 위한 반도체 소자의 제조방법에 한계가 발생하고 있다. 또한, 실리콘계 유전체를 대체하기 위하여 고유전 박막이 적용되면서 밴드갭으로 인한 누설 전류가 큰 폭으로 열화되는 문제점이 발생하고 있다.Due to the improvement in integration through the miniaturization of the line width of semiconductor devices, the space allowed for the implementation of capacitor structures is limited in terms of line width, and there are limitations in the manufacturing method of semiconductor devices for implementing capacitor structures using existing silicon-based dielectrics. In addition, as high dielectric thin films are applied to replace silicon-based dielectrics, a problem arises in which leakage current due to the band gap is significantly deteriorated.
이러한 문제점을 해결하기 위한 방안 중 하나로 고온 공정에서 박막을 형성함으로써 결정화 특성을 높이는 기술이 요구되며, 이를 위하여 박막 형성에 사용되는 전구체를 최적화할 필요가 있다.As one of the ways to solve this problem, a technology to increase crystallization characteristics by forming a thin film in a high temperature process is required, and for this, it is necessary to optimize the precursor used to form the thin film.
종래의 박막 형성을 위해 사용되던 전구체를 최적화하기 위한 방안의 일례로서, 유전율과 누설전류의 특성을 개선할 수 있는 다양한 도핑용 전구체들이 제시될 수 있다. 그러나 해당 전구체들은 열안정성이 낮거나 저휘발도 특성의 전구체가 대부분이다. 따라서 박막 형성용 전구체의 최적화를 위해서는 고내열성 및 고휘발성과 같은 전구체의 물성적 특성 향상이 매우 중요한 과제라 할 수 있다.As an example of a method for optimizing the precursor used to form a conventional thin film, various doping precursors that can improve dielectric constant and leakage current characteristics can be proposed. However, most of these precursors have low thermal stability or low volatility characteristics. Therefore, in order to optimize the precursor for thin film formation, improving the physical properties of the precursor, such as high heat resistance and high volatility, is a very important task.
본 발명은 상기와 같은 종래기술들을 감안하여 안출된 것으로, 박막 형성용 전구체로서 적합한 화학적 특성을 나타낼 수 있는 신규한 이트륨 또는 스칸듐 함유 박막 형성용 전구체를 제공하는 것을 그 목적으로 한다.The present invention was conceived in consideration of the above prior arts, and its purpose is to provide a novel yttrium- or scandium-containing thin film-forming precursor that can exhibit chemical properties suitable as a thin film-forming precursor.
또한, 고내열성, 및 고휘발성의 화학적 특성을 나타내며, 상온에서 액상 상태 또는 낮은 녹는점을 갖는 고체 상태이거나 용매에 용해도가 높은 고체 상태인 이트륨 또는 스칸듐 함유 박막 형성용 전구체를 제공하는 것을 그 목적으로 한다.In addition, the purpose is to provide a precursor for forming a thin film containing yttrium or scandium, which exhibits chemical properties of high heat resistance and high volatility, and is in a liquid state at room temperature, a solid state with a low melting point, or a solid state with high solubility in a solvent. do.
또한, 상기 전구체를 이용하여 박막을 형성하는 방법을 제공하는 것을 그 목적으로 한다.Additionally, the purpose is to provide a method of forming a thin film using the precursor.
또한, 상기 박막을 포함하는 반도체 소자를 제공하는 것을 그 목적으로 한다.Additionally, the object is to provide a semiconductor device including the thin film.
상기와 같은 과제를 해결하기 위한 본 발명의 박막 형성용 전구체는 하기 화학식 1로 표시되는 화합물을 포함하는 것을 특징으로 한다.The precursor for forming a thin film of the present invention to solve the above problems is characterized by containing a compound represented by the following formula (1).
[화학식 1][Formula 1]
상기 화학식 1에서,In Formula 1,
M은 이트륨(Y) 또는 스칸듐(Sc)이며, R1 내지 R8은 각각 독립적으로 수소원자이거나, C1-C6의 직쇄형, 분지형 또는 고리형 알킬기, 알케닐기, 알콕시기, 아민기 또는 실릴기이다.M is yttrium (Y) or scandium (Sc), and R 1 to R 8 are each independently a hydrogen atom, or a C 1 -C 6 straight-chain, branched or cyclic alkyl group, alkenyl group, alkoxy group, or amine group. Or it is a silyl group.
이때, 상기 화학식 1에서 R6 및 R8은 서로 상이한 C1-C6의 직쇄형, 분지형 또는 고리형 알킬기일 수 있다.At this time, in Formula 1, R 6 and R 8 may be different C 1 -C 6 straight-chain, branched, or cyclic alkyl groups.
또한, 상기 화학식 1에서 R1 내지 R5 중 2개 이상은 서로 상이한 C1-C6의 직쇄형, 분지형 또는 고리형 알킬기일 수 있다.Additionally, in Formula 1, two or more of R 1 to R 5 may be different C 1 -C 6 straight-chain, branched, or cyclic alkyl groups.
또한, 상기 화학식 1에서 R6 및 R8은 서로 상이한 C1-C6의 직쇄형, 분지형 또는 고리형 알킬기이거나, 또는, R1 내지 R5 중 2개 이상은 서로 상이한 C1-C6의 직쇄형, 분지형 또는 고리형 알킬기일 수 있다.In addition, in Formula 1, R 6 and R 8 are different C 1 -C 6 straight-chain, branched or cyclic alkyl groups, or at least two of R 1 to R 5 are different C 1 -C 6 alkyl groups. It may be a straight-chain, branched, or cyclic alkyl group.
또한, 상기 화학식 1에서 R1 내지 R5 중 어느 하나 또는 그 이상은 에틸기(Et) 또는 메틸기(Me)일 수 있다.Additionally, in Formula 1, one or more of R 1 to R 5 may be an ethyl group (Et) or a methyl group (Me).
또한, 상기 화학식 1에서 R6 및 R8 중 어느 하나 또는 그 이상은 C1-C6의 분지형 알킬기일 수 있다.Additionally, in Formula 1, one or more of R 6 and R 8 may be a C 1 -C 6 branched alkyl group.
또한, 상기 화학식 1에서 R6 및 R8 중 어느 하나 또는 그 이상은 t-부틸기(t-Bu), s-부틸기(sec-Bu), 이소부틸기(i-Bu), 이소프로필기(iPr), 또는 t-아밀기일 수 있다.In addition, in Formula 1, any one or more of R 6 and R 8 is a t-butyl group (t-Bu), s-butyl group (sec-Bu), isobutyl group (i-Bu), or isopropyl group. (iPr), or t-amyl group.
또한, 상기 화학식 1에서 R6 및 R8 중 어느 하나는 t-부틸기이며 다른 하나는 이소프로필기일 수 있다.Additionally, in Formula 1, one of R 6 and R 8 may be a t-butyl group and the other may be an isopropyl group.
또한, 상기 화학식 1에서 R7은 에틸기(Et), n-프로필기(n-Pr), n-부틸기(n-Bu), 이소프로필기(i-Pr), s-부틸기(sec-Bu) 또는 이소부틸기(i-Bu)일 수 있다.In addition, in Formula 1, R 7 is an ethyl group (Et), n-propyl group (n-Pr), n-butyl group (n-Bu), isopropyl group (i-Pr), s-butyl group (sec- Bu) or isobutyl group (i-Bu).
또한, 본 발명의 박막 형성 방법은 상기 박막 형성용 전구체를 이용하여 기판 상에 박막을 형성하는 공정을 포함하는 것을 특징으로 한다.In addition, the thin film forming method of the present invention is characterized by including a process of forming a thin film on a substrate using the thin film forming precursor.
이때, 상기 기판 상에 박막을 형성하는 공정은 기판의 표면에 상기 박막 형성용 전구체를 증착하여 전구체 박막을 형성하는 공정, 상기 전구체 박막을 반응성 가스와 반응시키는 공정을 포함할 수 있다.At this time, the process of forming a thin film on the substrate may include a process of forming a precursor thin film by depositing the thin film forming precursor on the surface of the substrate, and a process of reacting the precursor thin film with a reactive gas.
또한, 상기 반응성 가스는 질소(N2), 암모니아(NH3), 히드라진(N2H4), 아산화질소(N2O), 산소(O2), 수증기(H2O), 오존(O3), 과산화수소(H2O2), 실란(silane), 수소(H2), 다이보레인(B2H6) 중 어느 하나 또는 그 이상을 사용할 수 있다.In addition, the reactive gases include nitrogen (N 2 ), ammonia (NH 3 ), hydrazine (N 2 H 4 ), nitrous oxide (N 2 O), oxygen (O 2 ), water vapor (H 2 O), and ozone (O). 3 ), one or more of hydrogen peroxide (H 2 O 2 ), silane, hydrogen (H 2 ), and diborane (B 2 H 6 ) can be used.
또한, 상기 전구체 박막을 형성하는 공정은 상기 박막 형성용 전구체를 기화시켜 챔버 내부로 이송시키는 공정을 포함할 수 있다.Additionally, the process of forming the precursor thin film may include vaporizing the thin film forming precursor and transferring it into the chamber.
또한, 상기 증착은 SOD(spin-on dielectric, SOD) 공정, 저온 플라즈마(Low Temperature Plasma, LTP) 공정, 화학 기상 증착 (Chemical Vapor Deposition, CVD) 공정, 플라즈마 화학 기상 증착 (Plasma Enhanced Chemical Vapor Deposition, PECVD) 공정, 고밀도 플라즈마 화학 기상 증착(High Density Plasma -Chemical Vapor Deposition, HDPCVD) 공정, 원자층 증착(Atomic Layer Deposition, ALD) 공정, 또는 플라즈마 원자층 증착(Plasma-Enhanced Atomic Layer Deposition, PEALD) 공정 중 어느 하나에 의해 수행될 수 있다.In addition, the deposition is a spin-on dielectric (SOD) process, a low temperature plasma (LTP) process, a chemical vapor deposition (CVD) process, and a plasma enhanced chemical vapor deposition (CVD) process. PECVD) process, High Density Plasma -Chemical Vapor Deposition (HDPCVD) process, Atomic Layer Deposition (ALD) process, or Plasma-Enhanced Atomic Layer Deposition (PEALD) process. It can be performed by any one of the following.
또한, 상기 기판 상에 박막을 형성하는 공정은 상기 박막 형성용 전구체를 기판에 공급하고 플라즈마를 인가하여 박막을 형성하는 단계를 포함할 수 있다.Additionally, the process of forming a thin film on the substrate may include supplying the thin film forming precursor to the substrate and applying plasma to form the thin film.
또한, 본 발명의 반도체 소자는 상기 박막 형성 방법에 의해 제조된 박막을 포함하는 것을 특징으로 한다.Additionally, the semiconductor device of the present invention is characterized by including a thin film manufactured by the above thin film forming method.
본 발명에 따른 이트륨 또는 스칸듐 함유 박막 형성용 전구체는 비대칭 사이클로펜타디에닐 및 비대칭아미디네이트 리간드를 포함함으로써 전구체 화합물의 구조적 안정성이 우수하고, 고휘발성 및 고내열성의 특성을 나타내어 이트륨 또는 스칸듐 함유 박막 형성 공정에 사용하기 적합한 효과를 나타낸다.The precursor for forming a yttrium- or scandium-containing thin film according to the present invention contains an asymmetric cyclopentadienyl and an asymmetric amidinate ligand, so the precursor compound has excellent structural stability and exhibits high volatility and high heat resistance characteristics, thereby forming a yttrium- or scandium-containing thin film. It shows an effect suitable for use in the forming process.
또한, 상기 박막 형성용 전구체를 이용하여 고품질의 이트륨 또는 스칸듐 함유 박막을 형성할 수 있으며, 상기 박막 형성 방법에 의해 제조된 이트륨 또는 스칸듐 함유 함유 박막을 포함하는 반도체 소자를 제공할 수 있다.In addition, a high-quality yttrium- or scandium-containing thin film can be formed using the thin film forming precursor, and a semiconductor device including a yttrium- or scandium-containing thin film manufactured by the thin film forming method can be provided.
도 1은 비스(에틸사이클로펜타다이에닐)(이소프로필-t-부틸-메틸아미디네이토)이트륨의 1H NMR 분석결과이다.Figure 1 shows the 1 H NMR analysis results of bis(ethylcyclopentadienyl)(isopropyl-t-butyl-methylamidinato)yttrium.
도 2는 비스(에틸사이클로펜타다이에닐)(이소프로필-t-부틸-메틸아미디네이토)이트륨의 TGA 분석결과이다.Figure 2 shows the TGA analysis results of bis(ethylcyclopentadienyl)(isopropyl-t-butyl-methylamidinato)yttrium.
도 3은 비스(에틸사이클로펜타다이에닐)(이소프로필-t-부틸-메틸아미디네이토)이트륨의 DSC 분석결과이다.Figure 3 shows the DSC analysis results of bis(ethylcyclopentadienyl)(isopropyl-t-butyl-methylamidinato)yttrium.
도 4는 비스(에틸사이클로펜타다이에닐)(이소프로필-t-부틸-에틸아미디네이토)이트륨의 1H NMR 분석결과이다.Figure 4 shows the 1 H NMR analysis results of bis(ethylcyclopentadienyl)(isopropyl-t-butyl-ethylamidinato)yttrium.
도 5는 비스(다이에틸사이클로펜타다이에닐)(이소프로필-t-부틸-메틸아미디네이토)이트륨의 1H NMR 분석결과이다.Figure 5 shows the 1 H NMR analysis results of bis(diethylcyclopentadienyl)(isopropyl-t-butyl-methylamidinato)yttrium.
도 6은 비스(다이에틸사이클로펜타다이에닐)(이소프로필-t-부틸-메틸아미디네이토)이트륨의 TGA 분석결과이다.Figure 6 shows the TGA analysis results of bis(diethylcyclopentadienyl)(isopropyl-t-butyl-methylamidinato)yttrium.
도 7은 비스(다이에틸사이클로펜타다이에닐)(이소프로필-t-부틸-메틸아미디네이토)이트륨의 DSC 분석결과이다.Figure 7 shows the DSC analysis results of bis(diethylcyclopentadienyl)(isopropyl-t-butyl-methylamidinato)yttrium.
도 8은 비스(에틸메틸사이클로펜타다이에닐)(다이이소프로필-메틸아미디네이토)이트륨의 1H NMR 분석결과이다.Figure 8 shows the 1 H NMR analysis results of bis(ethylmethylcyclopentadienyl)(diisopropyl-methylamidinato)yttrium.
이하 본 발명을 보다 상세히 설명한다. 본 명세서 및 청구범위에 사용된 용어나 단어는 통상적이거나 사전적인 의미로 한정해서 해석되어서는 아니되며, 발명자는 그 자신의 발명을 가장 최선의 방법으로 설명하기 위해 용어의 개념을 적절하게 정의할 수 있다는 원칙에 입각하여 본 발명의 기술적 사상에 부합하는 의미와 개념으로 해석되어야만 한다.Hereinafter, the present invention will be described in more detail. Terms or words used in this specification and claims should not be construed as limited to their common or dictionary meanings, and the inventor may appropriately define the concept of terms in order to explain his or her invention in the best way. It must be interpreted with meaning and concept consistent with the technical idea of the present invention based on the principle that it is.
본 발명에 따른 박막 형성용 전구체는 이트륨 또는 스칸듐 함유 박막을 형성하기 위한 것으로서, 하기 화학식 1로 표시되는 화합물을 포함하는 것을 특징으로 한다.The precursor for forming a thin film according to the present invention is for forming a thin film containing yttrium or scandium, and is characterized by containing a compound represented by the following formula (1).
[화학식 1][Formula 1]
상기 화학식 1에서,In Formula 1,
M은 이트륨(Y) 또는 스칸듐(Sc)이며, R1 내지 R8은 각각 독립적으로 수소원자이거나, C1-C6의 직쇄형, 분지형 또는 고리형 알킬기, 알케닐기, 알콕시기, 아민기 또는 실릴기이다.M is yttrium (Y) or scandium (Sc), and R 1 to R 8 are each independently a hydrogen atom, or a C 1 -C 6 straight-chain, branched or cyclic alkyl group, alkenyl group, alkoxy group, or amine group. Or it is a silyl group.
상기 박막 형성용 전구체는 관능기의 종류에 따른 다양한 형태의 화합물을 형성할 수 있다.The precursor for forming the thin film can form various types of compounds depending on the type of functional group.
상기 화학식 1로 표시되는 화합물의 일 실시예에서는 R6 및 R8은 서로 상이한 C1-C6의 직쇄형, 분지형 또는 고리형 알킬기일 수 있다. 이러한 화학구조에서는 R6 및 R8의 서로 다른 형태에 의해 비대칭 구조를 형성할 수 있다.In one embodiment of the compound represented by Formula 1, R 6 and R 8 may be different C 1 -C 6 straight-chain, branched, or cyclic alkyl groups. In this chemical structure, an asymmetric structure can be formed by different forms of R 6 and R 8 .
또한, 상기 화학식 1에서 R1 내지 R5 중 2개 이상은 서로 상이한 C1-C6의 직쇄형, 분지형 또는 고리형 알킬기일 수 있으며, 이를 통해 비대칭 구조를 형성할 수 있다. Additionally, in Formula 1, two or more of R 1 to R 5 may be different C 1 -C 6 straight-chain, branched, or cyclic alkyl groups, thereby forming an asymmetric structure.
또한, 상기 화학식 1에서 R6 및 R8은 서로 상이한 C1-C6의 직쇄형, 분지형 또는 고리형 알킬기이거나, 또는, R1 내지 R5 중 2개 이상은 서로 상이한 C1-C6의 직쇄형, 분지형 또는 고리형 알킬기일 수 있으며, 이를 통해 화합물의 전반적인 구조적 비대칭성을 증가시킬 수 있다.In addition, in Formula 1, R 6 and R 8 are different C 1 -C 6 straight-chain, branched or cyclic alkyl groups, or at least two of R 1 to R 5 are different C 1 -C 6 alkyl groups. It may be a straight-chain, branched, or cyclic alkyl group, which can increase the overall structural asymmetry of the compound.
또한, 상기 화학식 1에서 R1 내지 R5 중 어느 하나 또는 그 이상은 에틸기(Et) 또는 메틸기(Me)일 수 있으며, R6 및 R8 중 어느 하나 또는 그 이상은 C1-C6의 분지형 알킬기일 수 있고, R6 및 R8 중 어느 하나 또는 그 이상은 t-부틸기(t-Bu), s-부틸기(sec-Bu), 이소부틸기(i-Bu), 이소프로필기(iPr), 또는 t-아밀기일 수도 있다. 또한, R6 및 R8 중 어느 하나는 t-부틸기이며 다른 하나는 이소프로필기일 수 있으며, R7은 에틸기(Et), n-프로필기(n-Pr), n-부틸기(n-Bu), 이소프로필기(i-Pr), s-부틸기(sec-Bu) 또는 이소부틸기(i-Bu)로 한정될 수도 있다.Additionally, in Formula 1, any one or more of R 1 to R 5 may be an ethyl group (Et) or a methyl group (Me), and one or more of R 6 and R 8 may be a C 1 -C 6 group. It may be a functional alkyl group, and one or more of R 6 and R 8 is a t-butyl group (t-Bu), s-butyl group (sec-Bu), isobutyl group (i-Bu), or isopropyl group. (iPr), or it may be a t-amyl group. In addition, one of R 6 and R 8 may be a t-butyl group and the other may be an isopropyl group, and R 7 may be an ethyl group (Et), an n-propyl group (n-Pr), or an n-butyl group (n- Bu), isopropyl group (i-Pr), s-butyl group (sec-Bu), or isobutyl group (i-Bu).
이와 같은 화학구조는 구조적 안정성이 우수하고, 고휘발성 및 고내열성의 물성을 나타내기 때문에 고품질의 박막을 형성하기에 적합한 것으로 파악되었다.This chemical structure was found to be suitable for forming a high-quality thin film because it has excellent structural stability and exhibits high volatility and high heat resistance properties.
또한, 본 발명의 박막 형성용 전구체는 박막 형성 공정의 조건 및 효율을 고려하여 전구체용 화합물의 용해 또는 희석을 위한 용매를 추가적으로 포함할 수 있다. 상기 용매로는 C1-C16의 포화 또는 불포화 탄화수소, 케톤, 에테르, 글라임, 에스테르, 테트라하이드로퓨란, 3차 아민 중 어느 하나 또는 이들의 혼합물을 사용할 수 있다. 상기 C1-C16의 포화 또는 불포화 탄화수소의 예로는 톨루엔, 헵탄 등을 들 수 있으며, 3차 아민으로는 디메틸에틸아민을 들 수 있다.In addition, the thin film forming precursor of the present invention may additionally include a solvent for dissolving or diluting the precursor compound in consideration of the conditions and efficiency of the thin film forming process. The solvent may be any one of C 1 -C 16 saturated or unsaturated hydrocarbons, ketones, ethers, glymes, esters, tetrahydrofuran, tertiary amines, or mixtures thereof. Examples of the C 1 -C 16 saturated or unsaturated hydrocarbon include toluene and heptane, and examples of the tertiary amine include dimethylethylamine.
특히, 화학구조에 따라 박막 형성용 전구체의 화합물이 실온에서 고체 상태일 수 있는데, 이 경우 상기 용매를 포함함으로써 상기 화합물을 용해할 수 있다. 즉, 상기 용매를 포함하는 경우, 상기 전구체 화합물을 용해할 수 있는 용매 및 함량으로 함유되게 되며, 상기 박막 형성용 전구체 총 중량에 대하여 1 내지 99 중량%로 포함되는 것이 바람직하다.In particular, depending on the chemical structure, the precursor compound for forming a thin film may be in a solid state at room temperature. In this case, the compound can be dissolved by including the solvent. That is, when the solvent is included, it is contained in a solvent and amount capable of dissolving the precursor compound, and is preferably contained in 1 to 99% by weight based on the total weight of the precursor for forming the thin film.
상기 용매를 포함하거나 포함하지 않는 형태의 박막 형성용 전구체를 이용하여 기판 상에 박막을 형성하게 된다. 구체적으로, 기판 상에 박막을 형성하는 공정은 기판의 표면에 상기 박막 형성용 전구체를 증착하여 전구체 박막을 형성하는 공정, 상기 전구체 박막을 반응성 가스와 반응시키는 공정을 포함할 수 있다.A thin film is formed on a substrate using a precursor for forming a thin film containing or not containing the solvent. Specifically, the process of forming a thin film on a substrate may include a process of forming a precursor thin film by depositing the thin film forming precursor on the surface of the substrate, and a process of reacting the precursor thin film with a reactive gas.
이때, 상기 반응성 가스는 질소(N2), 암모니아(NH3), 히드라진(N2H4), 아산화질소(N2O), 산소(O2), 수증기(H2O), 오존(O3), 과산화수소(H2O2), 실란(silane), 수소(H2), 다이보레인(B2H6) 중 어느 하나 또는 그 이상을 사용할 수 있다.At this time, the reactive gas is nitrogen (N 2 ), ammonia (NH 3 ), hydrazine (N 2 H 4 ), nitrous oxide (N 2 O), oxygen (O 2 ), water vapor (H 2 O), and ozone (O). 3 ), one or more of hydrogen peroxide (H 2 O 2 ), silane, hydrogen (H 2 ), and diborane (B 2 H 6 ) can be used.
상기 반응성 가스의 종류에 따라 이트륨 또는 스칸듐의 금속 박막, 산화물, 질화물, 산질화물 박막 등 다양한 형태의 박막을 형성할 수 있다.Depending on the type of the reactive gas, various types of thin films, such as yttrium or scandium metal thin films, oxide, nitride, and oxynitride thin films, can be formed.
또한, 상기 전구체 박막을 형성하는 공정은 상기 박막 형성용 전구체를 기화시켜 챔버 내부로 이송시키는 공정을 포함할 수 있는데, 이를 위하여 전술한 바와 같이 용매를 포함하는 전구체를 사용할 수도 있다. 또한, 상온에서 액상으로 존재하며 기화될 수 있는 경우에는 별도의 용매 없이도 챔버 내부로 상기 박막 형성용 전구체를 이송시킬 수 있다.Additionally, the process of forming the precursor thin film may include a process of vaporizing the thin film forming precursor and transferring it into the chamber. For this purpose, a precursor containing a solvent may be used as described above. Additionally, if it exists in a liquid state at room temperature and can be vaporized, the thin film forming precursor can be transported into the chamber without a separate solvent.
또한, 상기 증착은 SOD(spin-on dielectric, SOD) 공정, 저온 플라즈마(Low Temperature Plasma, LTP) 공정, 화학 기상 증착 (Chemical Vapor Deposition, CVD) 공정, 플라즈마 화학 기상 증착 (Plasma Enhanced Chemical Vapor Deposition, PECVD) 공정, 고밀도 플라즈마 화학 기상 증착(High Density Plasma -Chemical Vapor Deposition, HDP-CVD) 공정, 원자층 증착(Atomic Layer Deposition, ALD) 공정, 또는 플라즈마 원자층 증착(Plasma-Enhanced Atomic Layer Deposition, PEALD) 공정 중 어느 하나에 의해 수행될 수 있다. 예를 들어, HDP-CVD 공정을 적용할 경우 상압 화학 기상 증착 공정(AP-CVD), 저압 화학 기상 증착 공정(LP-CVD) 또는 플라즈마 강화 화학 기상 증착 공정(PE-CVD)에 비해 고진공 및 고파워에서 진행될 수 있기 때문에 구조적으로 치밀하고 기계적 특성이 우수한 박막을 형성할 수 있게 된다.In addition, the deposition is a spin-on dielectric (SOD) process, a low temperature plasma (LTP) process, a chemical vapor deposition (CVD) process, and a plasma enhanced chemical vapor deposition (CVD) process. PECVD) process, High Density Plasma -Chemical Vapor Deposition (HDP-CVD) process, Atomic Layer Deposition (ALD) process, or Plasma-Enhanced Atomic Layer Deposition (PEALD) ) can be performed by any one of the processes. For example, when applying the HDP-CVD process, the high vacuum and high Because it can be carried out at high power, it is possible to form a thin film that is structurally dense and has excellent mechanical properties.
또한, 기판 상에 박막을 형성하는 공정은 상기 박막 형성용 전구체를 기판에 공급하고 반응물의 존재 하에 플라즈마를 인가함으로써 금속, 산화물, 질화물, 산질화물 등의 박막을 형성하는 공정을 포함할 수 있다.Additionally, the process of forming a thin film on a substrate may include forming a thin film of a metal, oxide, nitride, oxynitride, etc. by supplying the thin film forming precursor to the substrate and applying plasma in the presence of a reactant.
또한, 상기 박막을 형성하는 공정은 1 내지 1000mTorr의 챔버 내 압력 조건에서 수행할 수 있다. 또한, 상기 챔버 내에 플라즈마를 형성하기 위한 소스 파워는 500 내지 9,000W, 바이어스 파워는 0 내지 5,000W가 적절하다. 또한, 상기 바이어스 파워는 경우에 따라서 가하지 않을 수도 있다.Additionally, the process of forming the thin film can be performed under chamber pressure conditions of 1 to 1000 mTorr. In addition, the source power for forming plasma in the chamber is 500 to 9,000 W, and the bias power is 0 to 5,000 W. Additionally, the bias power may not be applied depending on the case.
또한, 상기 기판 상에 박막을 형성하는 공정은 150 내지 500℃의 온도 범위에서 수행될 수 있다.Additionally, the process of forming a thin film on the substrate may be performed at a temperature range of 150 to 500°C.
또한, 상기 박막 형성용 전구체의 공급 시, 최종 형성되는 금속막에서의 전기적 특성, 즉 정전용량 또는 누설 전류값을 더욱 개선시키기 위하여 필요에 따라 제2 금속 전구체를 도입할 수도 있다. 상기 제2 금속 전구체는 규소(Si), 티타늄(Ti), 게르마늄(Ge), 스트론튬(Sr), 니오브(Nb), 바륨(Ba), 하프늄(Hf), 탄탈륨(Ta), 악티늄족(Ac) 원자로부터 선택된 1종 이상의 금속(M")을 포함하는 금속 전구체를 선택적으로 더 공급할 수도 있다. 상기 제2 금속 전구체는 상기 금속을 포함하는 알킬아미드계 화합물 또는 알콕시계 화합물 일 수 있다. 일례로 상기 금속이 Si인 경우 제2금속 전구체로 SiH(N(CH3)2)3, Si(N(C2H5)2)4, Si(N(C2H5)(CH3))4, Si(N(CH3)2)4, Si(OC4H9)4, Si(OC2H5)4, Si(OCH3)4, Si(OC(CH3)3)4 등이 사용될 수 있다.Additionally, when supplying the thin film forming precursor, a second metal precursor may be introduced as needed to further improve the electrical properties, that is, capacitance or leakage current value, of the final formed metal film. The second metal precursor is silicon (Si), titanium (Ti), germanium (Ge), strontium (Sr), niobium (Nb), barium (Ba), hafnium (Hf), tantalum (Ta), and actinium (Ac). ) A metal precursor containing one or more metals (M") selected from atoms may be optionally further supplied. The second metal precursor may be an alkylamide-based compound or an alkoxy-based compound containing the metal. For example, When the metal is Si, the second metal precursor is SiH(N(CH 3 ) 2 ) 3 , Si(N(C 2 H 5 ) 2 ) 4 , Si(N(C 2 H 5 )(CH 3 )) 4 , Si(N(CH 3 ) 2 ) 4 , Si(OC 4 H 9 ) 4 , Si(OC 2 H 5 ) 4 , Si(OCH 3 ) 4 , Si(OC(CH 3 ) 3 ) 4 , etc. can be used. You can.
상기 제2 금속 전구체의 공급은 상기 박막 형성용 전구체의 공급 방법과 동일한 방법으로 실시될 수 있으며, 상기 제2 금속 전구체는 상기 전구체와 함께 박막 형성용 기판 위로 공급될 수도 있고, 또는 전구체의 공급 완료 이후 순차적으로 공급될 수도 있다.The supply of the second metal precursor may be carried out in the same manner as the supply method of the thin film formation precursor, and the second metal precursor may be supplied together with the precursor onto the thin film formation substrate, or the supply of the precursor may be completed. It may then be supplied sequentially.
상기와 같은 박막 형성용 전구체 및 선택적으로 제2 금속 전구체는 상기 박막 형성용 기판과 접촉시키기 위해 반응 챔버 내로 공급되기 전까지 50 내지 250℃의 온도를 유지하는 것이 바람직하며, 보다 바람직하게는 100 내지 200℃의 온도를 유지하는 것이 좋다.The precursor for forming the thin film and optionally the second metal precursor as described above are preferably maintained at a temperature of 50 to 250° C. before being supplied into the reaction chamber for contact with the substrate for forming the thin film, more preferably 100 to 200° C. It is recommended to maintain a temperature of ℃.
또한, 전구체의 공급 단계 후 반응성 가스의 공급에 앞서, 상기 전구체 및 선택적으로 제2 금속 전구체의 기판 위로의 이동을 돕거나, 반응기 내가 증착에 적절한 압력을 갖도록 하며, 또한, 챔버 내에 존재하는 불순물 등을 외부로 방출시키기 위하여, 반응기 내에 아르곤(Ar), 질소(N2), 또는 헬륨(He) 등의 불활성 기체를 퍼지하는 공정이 실시될 수 있다. 이때 불활성 기체의 퍼지는 반응기내 압력이 1 내지 5 Torr가 되도록 실시되는 것이 바람직하다.In addition, after supplying the precursor and prior to supplying the reactive gas, it assists the movement of the precursor and optionally the second metal precursor onto the substrate, ensures an appropriate pressure for deposition within the reactor, and also helps remove impurities present in the chamber, etc. In order to release it to the outside, a process of purging an inert gas such as argon (Ar), nitrogen (N 2 ), or helium (He) may be performed in the reactor. At this time, it is preferable that the inert gas is spread so that the pressure inside the reactor is 1 to 5 Torr.
또한, 플라즈마 처리 외에 열처리 또는 광조사에 의한 처리 공정을 수행할 수도 있는데, 박막 형성용 전구체의 증착을 위한 열에너지를 제공하기 위한 것으로, 통상의 방법에 따라 실시될 수 있다. 바람직하게는, 충분한 성장 속도로, 목적하는 물리적 상태와 조성을 갖는 박막을 제조하기 위해서는 반응기내 기판의 온도가 100 내지 1,000℃, 바람직하게는 250 내지 400℃가 되도록 상기 처리 공정을 실시하는 것이 바람직하다.Additionally, in addition to plasma treatment, a heat treatment or light irradiation treatment process may be performed to provide heat energy for deposition of a thin film forming precursor, and may be performed according to a conventional method. Preferably, in order to produce a thin film having the desired physical state and composition at a sufficient growth rate, the treatment process is preferably performed so that the temperature of the substrate in the reactor is 100 to 1,000°C, preferably 250 to 400°C. .
또한, 상기 처리 공정 시에도 전술한 바와 같이 반응물의 기판 위로의 이동을 돕거나, 반응기 내가 증착에 적절한 압력을 갖도록 하며, 또한 반응기내 존재하는 불순물 또는 부산물 등을 외부로 방출시키기 위하여, 반응기 내에 아르곤(Ar), 질소(N2), 또는 헬륨(He) 등의 불활성 기체를 퍼지하는 공정이 실시될 수 있다.In addition, during the treatment process, as described above, argon is used in the reactor to help the reactant move onto the substrate, to maintain an appropriate pressure for deposition within the reactor, and to release impurities or by-products present in the reactor to the outside. A process of purging an inert gas such as (Ar), nitrogen (N 2 ), or helium (He) may be performed.
상기와 같은 박막 형성용 전구체의 투입, 반응물의 투입, 그리고 불활성 기체의 투입 처리 공정은 1 사이클로 하여. 1 사이클 이상 반복 실시함으로써 박막이 형성될 수 있다.The above process of adding the precursor for forming a thin film, adding the reactant, and adding the inert gas is one cycle. A thin film can be formed by repeating the process one or more cycles.
또한, 상기 박막 형성 공정을 적용하여 제조된 박막은 다양한 반도체 소자에 이용될 수 있다.Additionally, thin films manufactured by applying the thin film forming process can be used in various semiconductor devices.
이하, 실시예를 통하여 본 발명의 효과를 설명한다.Hereinafter, the effects of the present invention will be explained through examples.
[합성예 1] 비스(에틸사이클로펜타디에닐)이트륨 클로라이드[(EtCp)2YCl]의 합성[Synthesis Example 1] Synthesis of bis(ethylcyclopentadienyl)yttrium chloride [(EtCp) 2 YCl]
THF 300㎖와 에틸사이클로펜타디엔 48.22g(0.512mol) 용액에 n-BuLi 헥산 용액(2.5 M) 204.9㎖(0.512mol)를 -78℃에서 천천히 적가하고, 30분 동안 교반한 후 실온으로 승온하여, 2시간 동안 추가로 교반하여 Li-EtCp 용액을 제조하였다. 새로운 플라스크에 이트륨 클로라이드 50.0g(0.256mol)와 톨루엔 150㎖를 투입한 뒤, 교반하면서 -78℃로 냉각시켰다. 앞서 제조된 Li-EtCp 용액을 이트륨 클로라이드 혼합물을 함유하는 플라스크에 천천히 적가하고, -78℃에서 30분 동안 교반한 후 실온으로 승온하여 12시간 교반함으로써 비스(에틸사이클로펜타디에닐)이트륨 클로라이드를 합성하였다.To a solution of 300 ml of THF and 48.22 g (0.512 mol) of ethylcyclopentadiene, 204.9 ml (0.512 mol) of n-BuLi hexane solution (2.5 M) was slowly added dropwise at -78°C, stirred for 30 minutes, and then heated to room temperature. , and further stirred for 2 hours to prepare a Li-EtCp solution. 50.0 g (0.256 mol) of yttrium chloride and 150 ml of toluene were added to a new flask, and then cooled to -78°C while stirring. The previously prepared Li-EtCp solution was slowly added dropwise to the flask containing the yttrium chloride mixture, stirred at -78°C for 30 minutes, then raised to room temperature and stirred for 12 hours to synthesize bis(ethylcyclopentadienyl)yttrium chloride. did.
[합성예 2] 비스(에틸사이클로펜타디에닐)(아이소프로필-터셔리부틸-메틸아미디네이토)이트륨[(EtCp)2Y(iPrtBuMe-AMD)]의 합성[Synthesis Example 2] Synthesis of bis(ethylcyclopentadienyl)(isopropyl-tertiary butyl-methylamidinato)yttrium [(EtCp) 2 Y( i Pr t BuMe-AMD)]
THF 300㎖에 아이소프로필-t-부틸-메틸아미디네이트 40.02g(0.256mol)을 투입하고 -78℃로 냉각시킨 뒤, n-BuLi 헥산 용액(2.5M) 102.4㎖(0.256mol)를 천천히 적가하여 Li-(iPrtBuMe-AMD)를 제조하였다. 용액을 -78℃에서 30분 동안 교반 한 후 실온으로 가온하고, 실온에서 2시간 동안 추가로 교반하였다. 제조된 Li-(iPrtBuMe-AMD) 용액를 상온에서 (EtCp)2YCl을 함유하는 플라스크에 천천히 적가하여 상온에서 12시간 교반하였다. 혼합물을 진공 하에서 증발시키고, 펜탄 250㎖에 녹인 뒤 여과하여 용매 및 휘발물질을 진공 하에 증발시켰다. 생성된 적색 액체를 250℃ 및 32mTorr에서 연한 노랑색 고체를 얻었다. 수율은 55.4g(50.3%)이었다. NMR(Bruker사 AV400MHz HD) 분석결과는 도 1과 같으며, 특성 피크는 아래와 같다.Add 40.02 g (0.256 mol) of isopropyl-t-butyl-methylamidinate to 300 ml of THF, cool to -78°C, and then slowly add 102.4 ml (0.256 mol) of n-BuLi hexane solution (2.5 M) dropwise. Li-( i Pr t BuMe-AMD) was prepared. The solution was stirred at -78°C for 30 minutes, then warmed to room temperature, and stirred for an additional 2 hours at room temperature. The prepared Li-( i Pr t BuMe-AMD) solution was slowly added dropwise to a flask containing (EtCp) 2 YCl at room temperature and stirred at room temperature for 12 hours. The mixture was evaporated under vacuum, dissolved in 250 ml of pentane, filtered, and the solvent and volatile substances were evaporated under vacuum. The resulting red liquid was obtained as a light yellow solid at 250°C and 32mTorr. The yield was 55.4g (50.3%). The NMR (AV400MHz HD, Bruker company) analysis results are shown in Figure 1, and the characteristic peaks are as follows.
1H NMR (C6D6, 25℃): 0.97(d, 6H), 1.10(s, 9H), 1.25(t, 3H), 1.63(s, 3H), 2.54(q, 4H), 3.28(m, 1H), 6.08(dt, 8H). 1 H NMR (C 6 D 6 , 25°C): 0.97(d, 6H), 1.10(s, 9H), 1.25(t, 3H), 1.63(s, 3H), 2.54(q, 4H), 3.28( m, 1H), 6.08(dt, 8H).
연노랑 고체는 질소를 200㎖/분으로 유동시키는 분위기에서 10℃/분의 온도 상승 속도로 측정된 TGA(TA instrument사 SDT Q600) 분석 동안 1%로, 잔류 질량을 거의 남기지 않았다. 이러한 결과는 온도 변화에 따른 중량 손실 백분율을 나타내는 TGA 분석결과는 도 2와 같다.The light yellow solid left almost no residual mass at 1% during TGA (SDT Q600 from TA Instruments) analysis, which was measured at a temperature rise rate of 10°C/min in an atmosphere flowing nitrogen at 200 mL/min. These results are shown in Figure 2. The TGA analysis results showing the percentage of weight loss according to temperature change are shown in Figure 2.
연노랑 고체 샘플을 DSC용 밀폐 용기에 담아 40℃ 조건에서 10분을 유지한 뒤, 10℃/분의 온도 상승 속도로 측정된 DSC(TA instrument사 Discovery 25) 분석 동안 439℃에서 분해 피크가 관찰되었다. 이러한 결과는 온도 변화에 따른 열에너지 변화를 나타내는 DSC 분석결과는 도 3과 같다.The light yellow solid sample was placed in an airtight container for DSC and maintained at 40°C for 10 minutes, and then a decomposition peak was observed at 439°C during DSC (Discovery 25, TA instrument) analysis measured at a temperature rise rate of 10°C/min. . These results are shown in Figure 3. The DSC analysis results showing the change in thermal energy according to temperature change are shown in Figure 3.
[합성예 3] 비스(에틸사이클로펜타디에닐)(아이소프로필-터셔리부틸-에틸아미디네이토)이트륨[(EtCp)2Y(iPrtBuEt-AMD)]의 합성[Synthesis Example 3] Synthesis of bis(ethylcyclopentadienyl)(isopropyl-tertiary butyl-ethylamidinato)yttrium [(EtCp) 2 Y( i Pr t BuEt-AMD)]
THF 300㎖에 아이소프로필-터셔리부틸-에틸아미디네이트 43.61g(0.256mol)을 투입하고 -78℃로 냉각시킨 뒤, n-BuLi 헥산 용액(2.5M) 102.4㎖(0.256mol)를 천천히 적가하여 Li-(iPrtBuEt-AMD)를 제조하였다. 용액을 -78℃에서 30분 동안 교반 한 후 실온으로 가온하고, 실온에서 2시간 동안 추가로 교반하였다. 제조된 Li-(iPrtBuEt-AMD) 용액를 상온에서 (EtCp)2YCl을 함유하는 플라스크에 천천히 적가하여 상온에서 12시간 교반하였다. 혼합물을 진공 하에서 증발시키고, 펜탄 250㎖에 녹인 뒤 여과하여 용매 및 휘발물질을 진공 하에 증발시켰다. 생성된 적색 액체를 174℃ 및 36mTorr에서 분홍색 고체를 얻었다. 수율은 69.9g(61.4%)이었다. NMR(Bruker사 AV400MHz HD) 분석결과는 도 4와 같으며, 특성 피크는 아래와 같다.Add 43.61 g (0.256 mol) of isopropyl-tertiary butyl-ethylamidinate to 300 ml of THF, cool to -78°C, and then slowly add 102.4 ml (0.256 mol) of n-BuLi hexane solution (2.5 M) dropwise. Li-( i Pr t BuEt-AMD) was prepared. The solution was stirred at -78°C for 30 minutes, then warmed to room temperature, and stirred for an additional 2 hours at room temperature. The prepared Li-( i Pr t BuEt-AMD) solution was slowly added dropwise to a flask containing (EtCp) 2 YCl at room temperature and stirred at room temperature for 12 hours. The mixture was evaporated under vacuum, dissolved in 250 ml of pentane, filtered, and the solvent and volatile substances were evaporated under vacuum. The resulting red liquid was obtained as a pink solid at 174°C and 36 mTorr. The yield was 69.9g (61.4%). The NMR (AV400MHz HD, Bruker company) analysis results are shown in Figure 4, and the characteristic peaks are as follows.
1H NMR (C6D6, 25℃): 0.96(t, 3H), 1.00(d, 6H), 1.12(s, 9H), 1.25(t, 6H), 2.08(q, 2H), 2.56(q, 4H), 3.38(m, 1H), 6.10(dt, 8H). 1 H NMR (C 6 D 6 , 25°C): 0.96(t, 3H), 1.00(d, 6H), 1.12(s, 9H), 1.25(t, 6H), 2.08(q, 2H), 2.56( q, 4H), 3.38(m, 1H), 6.10(dt, 8H).
[합성예 4] 비스(다이에틸사이클로펜타디에닐)이트륨 클로라이드[(Et2Cp)2YCl]의 합성[Synthesis Example 4] Synthesis of bis(diethylcyclopentadienyl)yttrium chloride [(Et 2 Cp) 2 YCl]
THF 300㎖와 다이에틸사이클로펜타디엔 62.59g(0.512mol) 용액에 n-BuLi 헥산 용액(2.5 M) 204.9㎖(0.512mol)를 -78℃에서 천천히 적가하고, 30분 동안 교반한 후 실온으로 승온하여, 2시간 동안 추가로 교반하여 Li-Et2Cp 용액을 제조하였다. 새로운 플라스크에 이트륨 클로라이드 50.0g(0.256mol)와 Toluene 150㎖를 투입한 뒤, 교반하면서 -78℃로 냉각시켰다. 앞서 제조된 Li-Et2Cp 용액을 이트륨 클로라이드 혼합물을 함유하는 플라스크에 천천히 적가하고, -78℃에서 30분 동안 교반한 후 실온으로 승온하여 12시간 교반함으로써 비스(다이에틸사이클로펜타디에닐)이트륨 클로라이드를 합성하였다.To a solution of 300 ml of THF and 62.59 g (0.512 mol) of diethylcyclopentadiene, 204.9 ml (0.512 mol) of n-BuLi hexane solution (2.5 M) was slowly added dropwise at -78°C, stirred for 30 minutes, and then raised to room temperature. Then, the mixture was stirred for additional 2 hours to prepare a Li-Et 2 Cp solution. 50.0 g (0.256 mol) of yttrium chloride and 150 ml of toluene were added to a new flask, and then cooled to -78°C while stirring. The previously prepared Li-Et 2 Cp solution was slowly added dropwise to the flask containing the yttrium chloride mixture, stirred at -78°C for 30 minutes, then raised to room temperature and stirred for 12 hours to produce bis(diethylcyclopentadienyl)yttrium. Chloride was synthesized.
[합성예 5] 비스(다이에틸사이클로펜타디에닐)(아이소프로필-터셔리부틸-메틸아미디네이토)이트륨[(Et2Cp)2Y(iPrtBuMe-AMD)]의 합성[Synthesis Example 5] Synthesis of bis(diethylcyclopentadienyl)(isopropyl-tertiarybutyl-methylamidinato)yttrium [(Et 2 Cp) 2 Y( i Pr t BuMe-AMD)]
THF 300㎖에 아이소프로필-터셔리부틸-메틸아미디네이트 40.02g(0.256mol)을 투입하고 -78℃로 냉각시킨 뒤, n-BuLi 헥산 용액(2.5M) 102.4㎖(0.256mol)를 천천히 적가 하여 Li-(iPrtBuMe-AMD)를 제조하였다. 용액을 -78℃에서 30분 동안 교반 한 후 실온으로 가온 하고, 실온에서 2시간 동안 추가로 교반 하였다. 제조된 Li-(iPrtBuMe-AMD) 용액를 상온에서 (Et2Cp)2YCl을 함유하는 플라스크에 천천히 적가 하여 상온에서 12시간 교반하였다. 혼합물을 진공 하에서 증발시키고, 펜탄 250㎖에 녹인 뒤 여과하여 용매 및 휘발물질을 진공 하에 증발시켰다. 생성된 갈색 고체를 200℃ 및 27mTorr에서 연한 분홍색 고체를 얻었다. 수율은 94.2g(75.6%)이었다. NMR(Bruker사 AV400MHz HD) 분석결과는 도 5와 같으며, 특성 피크는 아래와 같다.Add 40.02 g (0.256 mol) of isopropyl-tertiary butyl-methylamidinate to 300 ml of THF, cool to -78°C, and then slowly add 102.4 ml (0.256 mol) of n-BuLi hexane solution (2.5 M) dropwise. Li-( i Pr t BuMe-AMD) was prepared. The solution was stirred at -78°C for 30 minutes, then warmed to room temperature, and stirred for an additional 2 hours at room temperature. The prepared Li-( i Pr t BuMe-AMD) solution was slowly added dropwise to a flask containing (Et 2 Cp) 2 YCl at room temperature and stirred at room temperature for 12 hours. The mixture was evaporated under vacuum, dissolved in 250 ml of pentane, filtered, and the solvent and volatile substances were evaporated under vacuum. The resulting brown solid was obtained at 200°C and 27 mTorr as a light pink solid. The yield was 94.2g (75.6%). The NMR (AV400MHz HD, Bruker company) analysis results are shown in Figure 5, and the characteristic peaks are as follows.
1H NMR (C6D6, 25℃): 1.02(d, 6H), 1.16(s, 9H), 1.26(m, 12H), 1.69(s, 3H), 2.55(m, 8H), 3.32(m, 1H), 6.00(m, 6H). 1 H NMR (C 6 D 6 , 25°C): 1.02(d, 6H), 1.16(s, 9H), 1.26(m, 12H), 1.69(s, 3H), 2.55(m, 8H), 3.32( m, 1H), 6.00(m, 6H).
연노랑 고체는 질소를 200㎖/분으로 유동시키는 분위기에서 10℃/분의 온도 상승 속도로 측정된 TGA(TA instrument사 SDT Q600) 분석 동안 1%로, 잔류 질량을 거의 남기지 않았다. 이러한 결과는 온도 변화에 따른 중량 손실 백분율을 나타내는 TGA 분석결과는 도 6과 같다.The light yellow solid left almost no residual mass at 1% during TGA (SDT Q600 from TA Instruments) analysis, which was measured at a temperature rise rate of 10°C/min in an atmosphere flowing nitrogen at 200 mL/min. These results are shown in Figure 6. The TGA analysis results showing the percentage of weight loss according to temperature change are shown in Figure 6.
연노랑 고체 샘플을 DSC용 밀폐 용기에 담아 40℃ 조건에서 10분을 유지한 뒤, 10℃/분의 온도 상승 속도로 측정된 DSC(TA instrument사 Discovery 25) 분석 동안 400℃ 이상에서 분해 피크가 관찰되었다. 이러한 결과는 온도 변화에 따른 열에너지 변화를 나타내는 DSC 분석결과는 도 7과 같다.The light yellow solid sample was placed in an airtight container for DSC and kept at 40℃ for 10 minutes, and then a decomposition peak was observed above 400℃ during DSC (Discovery 25, TA instrument) analysis measured at a temperature rise rate of 10℃/min. It has been done. These results are shown in Figure 7. The DSC analysis results showing the change in thermal energy according to the temperature change are shown in Figure 7.
[합성예 6] 비스(에틸,메틸사이클로펜타디에닐)이트륨 클로라이드[(EtCp)2YCl]의 합성[Synthesis Example 6] Synthesis of bis(ethyl,methylcyclopentadienyl)yttrium chloride [(EtCp) 2 YCl]
THF 300㎖와 에틸,메틸사이클로펜타디엔 55.40g(0.512mol) 용액에 n-BuLi 헥산 용액(2.5 M) 204.9㎖(0.512mol)를 -78℃에서 천천히 적가하고, 30분 동안 교반한 후 실온으로 승온하여, 2시간 동안 추가로 교반하여 Li-EtMeCp 용액을 제조하였다. 새로운 플라스크에 이트륨 클로라이드 50.0g(0.256mol)와 톨루엔 150㎖를 투입한 뒤, 교반하면서 -78℃로 냉각시켰다. 앞서 제조된 Li-EtMeCp 용액을 이트륨 클로라이드 혼합물을 함유하는 플라스크에 천천히 적가하고, -78℃에서 30분 동안 교반한 후 실온으로 승온하여 12시간 교반함으로써 비스(에틸메틸사이클로펜타디에닐)이트륨 클로라이드를 합성하였다.To a solution of 300 ml of THF and 55.40 g (0.512 mol) of ethyl, methylcyclopentadiene, 204.9 ml (0.512 mol) of n-BuLi hexane solution (2.5 M) was slowly added dropwise at -78°C, stirred for 30 minutes, and then cooled to room temperature. The temperature was raised and stirred for additional 2 hours to prepare a Li-EtMeCp solution. 50.0 g (0.256 mol) of yttrium chloride and 150 ml of toluene were added to a new flask, and then cooled to -78°C while stirring. The previously prepared Li-EtMeCp solution was slowly added dropwise to the flask containing the yttrium chloride mixture, stirred at -78°C for 30 minutes, then raised to room temperature and stirred for 12 hours to produce bis(ethylmethylcyclopentadienyl)yttrium chloride. synthesized.
[합성예 7] 비스(에틸메틸사이클로펜타디에닐)(다이아이소프로필-메틸아미디네이토)이트륨[(Et2Cp)2Y(iPr2Me-AMD)]의 합성[Synthesis Example 7] Synthesis of bis(ethylmethylcyclopentadienyl)(diisopropyl-methylamidinato)yttrium [(Et 2 Cp) 2 Y( i Pr 2 Me-AMD)]
THF 300㎖에 다이아이소프로필카보다이이미드 32.32g(0.256mol)을 투입하고 -78℃로 냉각시킨 뒤, MeLi 다이에틸이써 용액(1.6M) 160.0㎖(0.256mol)를 천천히 적가하여 Li-(iPr2Me-AMD)를 제조하였다. 용액을 -78℃에서 30분 동안 교반 한 후 실온으로 가온하고, 실온에서 2시간 동안 추가로 교반하였다. 제조된 Li-(iPr2Me-AMD) 용액를 상온에서 (EtMeCp)2YCl을 함유하는 플라스크에 천천히 적가하여 상온에서 12시간 교반하였다. 혼합물을 진공 하에서 증발시키고, 펜탄 250㎖에 녹인 뒤 여과하여 용매 및 휘발물질을 진공 하에 증발시켰다. 연한 노랑색 액체를 210℃ 및 98mTorr에서 붉은색 고체와 액체 혼합물을 얻었다. 수율은 68.9g(56.9%)이었다. NMR(Bruker사 AV400MHz HD) 분석결과는 도 8과 같으며, 특성 피크는 아래와 같다.Add 32.32 g (0.256 mol) of diisopropyl carbodiimide to 300 ml of THF and cool to -78°C. Then, 160.0 ml (0.256 mol) of MeLi diethyl solution (1.6 M) was slowly added dropwise to form Li-( i Pr 2 Me-AMD) was prepared. The solution was stirred at -78°C for 30 minutes, then warmed to room temperature, and stirred for an additional 2 hours at room temperature. The prepared Li-( iPr 2 Me-AMD) solution was slowly added dropwise to a flask containing (EtMeCp) 2 YCl at room temperature and stirred at room temperature for 12 hours. The mixture was evaporated under vacuum, dissolved in 250 ml of pentane, filtered, and the solvent and volatile substances were evaporated under vacuum. A light yellow liquid was obtained as a red solid and liquid mixture at 210°C and 98 mTorr. The yield was 68.9g (56.9%). The NMR (AV400MHz HD from Bruker) analysis results are shown in Figure 8, and the characteristic peaks are as follows.
1H NMR (C6D6, 25℃): 1.00(d, 12H), 1.21(m, 6H), 1.54(s, 3H), 2.119(m, 6H), 2.52(m, 4H), 3.31(m, 1H), 6.00(m, 6H). 1 H NMR (C 6 D 6 , 25°C): 1.00(d, 12H), 1.21(m, 6H), 1.54(s, 3H), 2.119(m, 6H), 2.52(m, 4H), 3.31( m, 1H), 6.00(m, 6H).
본 발명은 상술한 바와 같이 바람직한 실시형태를 들어 설명하였으나, 상기 실시형태들에 한정되지 아니하며 본 발명의 정신을 벗어나지 않는 범위 내에서 당해 발명이 속하는 기술분야에서 통상의 지식을 가진 자에 의해 다양한 변형과 변경이 가능하다. 그러한 변형예 및 변경예는 본 발명과 첨부된 특허청구범위의 범위 내에 속하는 것으로 보아야 한다.The present invention has been described with reference to preferred embodiments as described above, but is not limited to the above embodiments and may be modified in various ways by those skilled in the art without departing from the spirit of the invention. and can be changed. Such modifications and variations should be considered to fall within the scope of the present invention and the appended claims.
Claims (16)
- 하기 화학식 1로 표시되는 화합물을 포함하는 것을 특징으로 하는 박막 형성용 전구체.A precursor for forming a thin film, characterized in that it contains a compound represented by the following formula (1).[화학식 1][Formula 1]상기 화학식 1에서,In Formula 1,M은 이트륨(Y) 또는 스칸듐(Sc)이며, R1 내지 R8은 각각 독립적으로 수소원자이거나, C1-C6의 직쇄형, 분지형 또는 고리형 알킬기, 알케닐기, 알콕시기, 아민기 또는 실릴기이다.M is yttrium (Y) or scandium (Sc), and R 1 to R 8 are each independently a hydrogen atom, or a C 1 -C 6 straight-chain, branched or cyclic alkyl group, alkenyl group, alkoxy group, or amine group. Or it is a silyl group.
- 청구항 1에 있어서,In claim 1,상기 화학식 1에서 R6 및 R8은 서로 상이한 C1-C6의 직쇄형, 분지형 또는 고리형 알킬기인 것을 특징으로 하는 박막 형성용 전구체.In Formula 1, R 6 and R 8 are different C 1 -C 6 straight chain, branched or cyclic alkyl groups.
- 청구항 1에 있어서,In claim 1,상기 화학식 1에서 R1 내지 R5 중 2개 이상은 서로 상이한 C1-C6의 직쇄형, 분지형 또는 고리형 알킬기인 것을 특징으로 하는 박막 형성용 전구체.A precursor for forming a thin film, wherein at least two of R 1 to R 5 in Formula 1 are different C 1 -C 6 straight-chain, branched, or cyclic alkyl groups.
- 청구항 1에 있어서,In claim 1,상기 화학식 1에서 R6 및 R8은 서로 상이한 C1-C6의 직쇄형, 분지형 또는 고리형 알킬기이거나, 또는, R1 내지 R5 중 2개 이상은 서로 상이한 C1-C6의 직쇄형, 분지형 또는 고리형 알킬기인 것을 특징으로 하는 박막 형성용 전구체.In Formula 1, R 6 and R 8 are different C 1 -C 6 linear, branched or cyclic alkyl groups, or at least two of R 1 to R 5 are different C 1 -C 6 straight alkyl groups. A precursor for forming a thin film, characterized in that it is a chain-shaped, branched, or cyclic alkyl group.
- 청구항 1에 있어서,In claim 1,상기 화학식 1에서 R1 내지 R5 중 어느 하나 또는 그 이상은 에틸기(Et) 또는 메틸기(Me)인 것을 특징으로 하는 박막 형성용 전구체.A precursor for forming a thin film, wherein one or more of R 1 to R 5 in Formula 1 is an ethyl group (Et) or a methyl group (Me).
- 청구항 1에 있어서,In claim 1,상기 화학식 1에서 R6 및 R8 중 어느 하나 또는 그 이상은 C1-C6의 분지형 알킬기인 것을 특징으로 하는 박막 형성용 전구체.In Formula 1, any one or more of R 6 and R 8 is a C 1 -C 6 branched alkyl group.
- 청구항 1에 있어서,In claim 1,상기 화학식 1에서 R6 및 R8 중 어느 하나 또는 그 이상은 t-부틸기(t-Bu), s-부틸기(sec-Bu), 이소부틸기(i-Bu), 이소프로필기(iPr), 또는 t-아밀기인 것을 특징으로 하는 박막 형성용 전구체.In Formula 1, one or more of R 6 and R 8 are t-butyl group (t-Bu), s-butyl group (sec-Bu), isobutyl group (i-Bu), and isopropyl group (iPr). ), or a precursor for forming a thin film, characterized in that it is a t-amyl group.
- 청구항 1에 있어서,In claim 1,상기 화학식 1에서 R6 및 R8 중 어느 하나는 t-부틸기이며 다른 하나는 이소프로필기인 것을 특징으로 하는 박막 형성용 전구체.In Formula 1, one of R 6 and R 8 is a t-butyl group and the other is an isopropyl group.
- 청구항 1에 있어서,In claim 1,상기 화학식 1에서 R7은 에틸기(Et), n-프로필기(n-Pr), n-부틸기(n-Bu), 이소프로필기(i-Pr), s-부틸기(sec-Bu) 또는 이소부틸기(i-Bu)인 것을 특징으로 하는 박막 형성용 전구체.In Formula 1, R 7 is an ethyl group (Et), n-propyl group (n-Pr), n-butyl group (n-Bu), isopropyl group (i-Pr), and s-butyl group (sec-Bu). Or a precursor for forming a thin film, characterized in that it is an isobutyl group (i-Bu).
- 청구항 1 내지 9 중 어느 한 항에 따른 박막 형성용 전구체를 이용하여 기판 상에 박막을 형성하는 공정을 포함하는 것을 특징으로 하는 박막 형성 방법.A thin film forming method comprising a step of forming a thin film on a substrate using the thin film forming precursor according to any one of claims 1 to 9.
- 청구항 10에 있어서,In claim 10,상기 기판 상에 박막을 형성하는 공정은,The process of forming a thin film on the substrate is,기판의 표면에 상기 박막 형성용 전구체를 증착하여 전구체 박막을 형성하는 공정;A process of forming a precursor thin film by depositing the thin film forming precursor on the surface of a substrate;상기 전구체 박막을 반응성 가스와 반응시키는 공정;A process of reacting the precursor thin film with a reactive gas;을 포함하는 것을 특징으로 하는 박막 형성 방법.A thin film forming method comprising:
- 청구항 11에 있어서,In claim 11,상기 반응성 가스는 질소(N2), 암모니아(NH3), 히드라진(N2H4), 아산화질소(N2O), 산소(O2), 수증기(H2O), 오존(O3), 과산화수소(H2O2), 실란(silane), 수소(H2), 다이보레인(B2H6) 중 어느 하나 또는 그 이상인 것을 특징으로 하는 박막 형성 방법.The reactive gases include nitrogen (N 2 ), ammonia (NH 3 ), hydrazine (N 2 H 4 ), nitrous oxide (N 2 O), oxygen (O 2 ), water vapor (H 2 O), and ozone (O 3 ). , Hydrogen peroxide (H 2 O 2 ), silane, hydrogen (H 2 ), and diborane (B 2 H 6 ). A method of forming a thin film, characterized in that one or more of the following.
- 청구항 11에 있어서,In claim 11,상기 전구체 박막을 형성하는 공정은 상기 박막 형성용 전구체를 기화시켜 챔버 내부로 이송시키는 공정을 포함하는 것을 특징으로 하는 박막 형성 방법.The process of forming the precursor thin film includes vaporizing the precursor for forming the thin film and transferring it into the chamber.
- 청구항 11에 있어서,In claim 11,상기 증착은 SOD(spin-on dielectric, SOD) 공정, 저온 플라즈마(Low Temperature Plasma, LTP) 공정, 화학 기상 증착 (Chemical Vapor Deposition, CVD) 공정, 플라즈마 화학 기상 증착 (Plasma Enhanced Chemical Vapor Deposition, PECVD) 공정, 고밀도 플라즈마 화학 기상 증착(High Density Plasma -Chemical Vapor Deposition, HDPCVD) 공정, 원자층 증착(Atomic Layer Deposition, ALD) 공정, 또는 플라즈마 원자층 증착(Plasma-Enhanced Atomic Layer Deposition, PEALD) 공정 중 어느 하나에 의해 수행되는 것을 특징으로 하는 박막 형성 방법.The deposition includes a spin-on dielectric (SOD) process, a low temperature plasma (LTP) process, a chemical vapor deposition (CVD) process, and a plasma enhanced chemical vapor deposition (PECVD) process. process, High Density Plasma -Chemical Vapor Deposition (HDPCVD) process, Atomic Layer Deposition (ALD) process, or Plasma-Enhanced Atomic Layer Deposition (PEALD) process. A thin film forming method characterized in that it is carried out by one.
- 청구항 10에 있어서,In claim 10,상기 기판 상에 박막을 형성하는 공정은,The process of forming a thin film on the substrate is,상기 박막 형성용 전구체를 기판에 공급하고 플라즈마를 인가하여 박막을 형성하는 단계를 포함하는 것을 특징으로 하는 박막 형성 방법.A thin film forming method comprising supplying the thin film forming precursor to a substrate and applying plasma to form a thin film.
- 청구항 10의 박막 형성 방법에 의해 제조된 박막을 포함하는 것을 특징으로 하는 반도체 소자.A semiconductor device comprising a thin film manufactured by the thin film forming method of claim 10.
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US20160315168A1 (en) * | 2016-06-30 | 2016-10-27 | L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude | Process for forming gate insulators for tft structures |
KR20170063092A (en) * | 2015-11-30 | 2017-06-08 | 삼성전자주식회사 | Methods of forming thin film and integrated circuit device using niobium compound |
KR20190109142A (en) * | 2018-03-16 | 2019-09-25 | 삼성전자주식회사 | Lanthanum compound and methods of forming thin film and integrated circuit device |
KR20210084297A (en) * | 2019-12-27 | 2021-07-07 | 주식회사 유피케미칼 | Yttrium/lanthanide-containing precursor compounds, precursor compositions including the same for forming films, and method of forming yttrium/lanthanide-containing films using the precursor composition |
WO2022106508A1 (en) * | 2020-11-20 | 2022-05-27 | Merck Patent Gmbh | Lanthanide and lanthanide-like transition metal complexes |
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KR20170063092A (en) * | 2015-11-30 | 2017-06-08 | 삼성전자주식회사 | Methods of forming thin film and integrated circuit device using niobium compound |
US20160315168A1 (en) * | 2016-06-30 | 2016-10-27 | L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude | Process for forming gate insulators for tft structures |
KR20190109142A (en) * | 2018-03-16 | 2019-09-25 | 삼성전자주식회사 | Lanthanum compound and methods of forming thin film and integrated circuit device |
KR20210084297A (en) * | 2019-12-27 | 2021-07-07 | 주식회사 유피케미칼 | Yttrium/lanthanide-containing precursor compounds, precursor compositions including the same for forming films, and method of forming yttrium/lanthanide-containing films using the precursor composition |
WO2022106508A1 (en) * | 2020-11-20 | 2022-05-27 | Merck Patent Gmbh | Lanthanide and lanthanide-like transition metal complexes |
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