JP2023535086A - 有機金属化合物、これを含む前駆体組成物、およびこれを用いた薄膜の製造方法 - Google Patents
有機金属化合物、これを含む前駆体組成物、およびこれを用いた薄膜の製造方法 Download PDFInfo
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- 239000010409 thin film Substances 0.000 title claims abstract description 52
- 239000002243 precursor Substances 0.000 title claims abstract description 47
- 239000000203 mixture Substances 0.000 title claims abstract description 27
- 150000002902 organometallic compounds Chemical class 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 49
- 238000007740 vapor deposition Methods 0.000 claims abstract description 20
- 238000000231 atomic layer deposition Methods 0.000 claims abstract description 18
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 10
- 239000001257 hydrogen Substances 0.000 claims description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims description 27
- 125000004432 carbon atom Chemical group C* 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 18
- 150000002431 hydrogen Chemical class 0.000 claims description 18
- 229910052748 manganese Inorganic materials 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 13
- -1 methylsilyl group Chemical group 0.000 claims description 12
- 229910052802 copper Inorganic materials 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 8
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 8
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 8
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 8
- 239000012495 reaction gas Substances 0.000 claims description 8
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 8
- 229910052742 iron Inorganic materials 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
- 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
- 125000004429 atom Chemical group 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 125000005103 alkyl silyl group Chemical group 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 238000001947 vapour-phase growth Methods 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 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
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 229910000077 silane Inorganic materials 0.000 claims description 3
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 125000002524 organometallic group Chemical group 0.000 abstract description 23
- 230000009257 reactivity Effects 0.000 abstract description 9
- 238000000427 thin-film deposition Methods 0.000 abstract description 8
- 239000011572 manganese Substances 0.000 description 46
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 26
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 14
- 238000004455 differential thermal analysis Methods 0.000 description 12
- 239000007789 gas Substances 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 239000010949 copper Substances 0.000 description 9
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 8
- 239000003446 ligand Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000000151 deposition Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 150000004703 alkoxides Chemical class 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000000277 atomic layer chemical vapour deposition Methods 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000004518 low pressure chemical vapour deposition Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 229960005235 piperonyl butoxide Drugs 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- IUBQJLUDMLPAGT-UHFFFAOYSA-N potassium bis(trimethylsilyl)amide Chemical compound C[Si](C)(C)N([K])[Si](C)(C)C IUBQJLUDMLPAGT-UHFFFAOYSA-N 0.000 description 3
- 238000003828 vacuum filtration Methods 0.000 description 3
- IIJSFQFJZAEKHB-UHFFFAOYSA-M 1,3-dimethylimidazol-1-ium;chloride Chemical compound [Cl-].CN1C=C[N+](C)=C1 IIJSFQFJZAEKHB-UHFFFAOYSA-M 0.000 description 2
- BMQZYMYBQZGEEY-UHFFFAOYSA-M 1-ethyl-3-methylimidazolium chloride Chemical compound [Cl-].CCN1C=C[N+](C)=C1 BMQZYMYBQZGEEY-UHFFFAOYSA-M 0.000 description 2
- JOLFMOZUQSZTML-UHFFFAOYSA-M 1-methyl-3-propylimidazol-1-ium;chloride Chemical compound [Cl-].CCCN1C=C[N+](C)=C1 JOLFMOZUQSZTML-UHFFFAOYSA-M 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910017028 MnSi Inorganic materials 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 150000002697 manganese compounds Chemical class 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 229910021332 silicide Inorganic materials 0.000 description 2
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 2
- IIKLZLSFVWKBGX-UHFFFAOYSA-N CCC(C)O[Mn](C1N(C)C=CN1C)(C1N(C)C=CN1C)OC(C)CC Chemical compound CCC(C)O[Mn](C1N(C)C=CN1C)(C1N(C)C=CN1C)OC(C)CC IIKLZLSFVWKBGX-UHFFFAOYSA-N 0.000 description 1
- NPXHFKQKUWOZFM-UHFFFAOYSA-N CCC(C)O[Mn](C1N(CC)C=CN1C)(C1N(CC)C=CN1C)OC(C)CC Chemical compound CCC(C)O[Mn](C1N(CC)C=CN1C)(C1N(CC)C=CN1C)OC(C)CC NPXHFKQKUWOZFM-UHFFFAOYSA-N 0.000 description 1
- VQVJUGLLRLZMOJ-UHFFFAOYSA-N CCCN1C=CN(C)C1[Mn](C1N(CCC)C=CN1C)(N([Si](C)(C)C)[Si](C)(C)C)N([Si](C)(C)C)[Si](C)(C)C Chemical compound CCCN1C=CN(C)C1[Mn](C1N(CCC)C=CN1C)(N([Si](C)(C)C)[Si](C)(C)C)N([Si](C)(C)C)[Si](C)(C)C VQVJUGLLRLZMOJ-UHFFFAOYSA-N 0.000 description 1
- SEQYWGKRIILVFR-UHFFFAOYSA-N CCCN1C=CN(C)C1[Mn](C1N(CCC)C=CN1C)(OC(C)CC)OC(C)CC Chemical compound CCCN1C=CN(C)C1[Mn](C1N(CCC)C=CN1C)(OC(C)CC)OC(C)CC SEQYWGKRIILVFR-UHFFFAOYSA-N 0.000 description 1
- NUTUSRJZOHZGOJ-UHFFFAOYSA-N CCN1C=CN(C)C1[Mn](C1N(CC)C=CN1C)(N([Si](C)(C)C)[Si](C)(C)C)N([Si](C)(C)C)[Si](C)(C)C Chemical compound CCN1C=CN(C)C1[Mn](C1N(CC)C=CN1C)(N([Si](C)(C)C)[Si](C)(C)C)N([Si](C)(C)C)[Si](C)(C)C NUTUSRJZOHZGOJ-UHFFFAOYSA-N 0.000 description 1
- UKVRMQQWKFYPDH-UHFFFAOYSA-N CN1C=CN(C)C1[Mn](C1N(C)C=CN1C)(N([Si](C)(C)C)[Si](C)(C)C)N([Si](C)(C)C)[Si](C)(C)C Chemical compound CN1C=CN(C)C1[Mn](C1N(C)C=CN1C)(N([Si](C)(C)C)[Si](C)(C)C)N([Si](C)(C)C)[Si](C)(C)C UKVRMQQWKFYPDH-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- RRZKHZBOZDIQJG-UHFFFAOYSA-N azane;manganese Chemical compound N.[Mn] RRZKHZBOZDIQJG-UHFFFAOYSA-N 0.000 description 1
- XGIUDIMNNMKGDE-UHFFFAOYSA-N bis(trimethylsilyl)azanide Chemical compound C[Si](C)(C)[N-][Si](C)(C)C XGIUDIMNNMKGDE-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 230000005294 ferromagnetic effect Effects 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Classifications
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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
- C07F13/00—Compounds containing elements of Groups 7 or 17 of the Periodic Table
-
- 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
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/06—Cobalt compounds
-
- 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
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/06—Cobalt compounds
- C07F15/065—Cobalt compounds without a metal-carbon linkage
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/34—Nitrides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
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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
- C23C16/42—Silicides
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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
- C23C16/455—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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- Chemical & Material Sciences (AREA)
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- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
Description
aは、2であり;bは、1または2であり(ただし、MがCoの場合、bは、2ではない);
R1およびR2は、それぞれ独立して、水素、または炭素数1乃至4の線状もしくは分枝状アルキル基であり;R3は、-OR4または-NR5R6であり;
R4は、水素、または炭素数1乃至4の線状もしくは分枝状アルキル基であり;
R5およびR6は、それぞれ独立して、水素、炭素数1乃至4の線状もしくは分枝状アルキル基、または炭素数1乃至6の線状もしくは分枝状アルキルシリル基である。
本願のさらに他の側面は、前記気相蒸着用前駆体組成物をチャンバに導入するステップを含む薄膜の製造方法を提供する。
本願のさらに他の側面は、前記気相蒸着用前駆体組成物を用いて製造された有機金属含有薄膜を提供する。
また、本発明の気相蒸着用前駆体組成物は、熱的安定性および反応性が高くて、優れた薄膜物性、厚さおよび段差被覆性の確保が可能である。
前記のような物性は原子層蒸着法および化学気相蒸着法に適した有機金属前駆体を提供し、優れた薄膜特性に寄与する。
aは、2であり;bは、1または2であり(ただし、MがCoの場合、bは、2ではない);
R1およびR2は、それぞれ独立して、水素、または炭素数1乃至4の線状もしくは分枝状アルキル基であり;R3は、-OR4または-NR5R6であり;
R4は、水素、または炭素数1乃至4の線状もしくは分枝状アルキル基であり;
R5およびR6は、それぞれ独立して、水素、炭素数1乃至4の線状もしくは分枝状アルキル基、または炭素数1乃至6の線状もしくは分枝状アルキルシリル基であることが好ましい。
択されるいずれか1つであってもよいが、これに限定されるものではない。
例えば、R1、R2およびR4は、それぞれ独立して、水素、メチル基、エチル基、n-プロピル基、iso-プロピル基、n-ブチル基、iso-ブチル基、sec-ブチル基、およびtert-ブチル基からなる群より選択されるいずれか1つであることがさらに好ましい。
ジ-sec-ブトキシ-ビス(1,3-ジメチル-2,3-ジヒドロ-1H-イミダゾール-2-イル)マンガン[Mn(MeMeIz)2(secBuO)2];
ジ-sec-ブトキシ-ビス(1-エチル-3-メチル-2,3-ジヒドロ-1H-イミダゾール-2-イル)マンガン[Mn(MeEtIz)2(secBuO)2];
ジ-sec-ブトキシ-ビス(1-メチル-3-プロピル-2,3-ジヒドロ-1H-イミダゾール-2-イル)マンガン[Mn(MePrIz)2(secBuO)2]。
ビス(ビス(トリメチルシリル)アミノ)-ビス(1,3-ジメチル-2,3-ジヒドロ-1H-イミダゾール-2-イル)マンガン[Mn(MeMeIz)2(btsa)2];
ビス(ビス(トリメチルシリル)アミノ)-ビス(1-エチル-3-メチル-2,3-ジヒドロ-1H-イミダゾール-2-イル)マンガン[Mn(MeEtIz)2(btsa)2];
ビス(ビス(トリメチルシリル)アミノ)-ビス(1-メチル-3-プロピル-2,3-ジヒドロ-1H-イミダゾール-2-イル)マンガン[Mn(MePrIz)2(btsa)2]。
るために、反応ガスとして、アンモニア(NH3)またはヒドラジン(N2H4)を使用することができる。
シュレンクフラスコに、MnCl2(1当量、13g)、1,3-ジメチルイミダゾリウムクロライド(2当量)、カリウム2-ブトキシド(4当量)およびテトラヒドロフラン(THF)を入れて、室温で一晩撹拌した後、反応を終了させ、減圧ろ過して溶媒を除去した。得られた化合物を70℃および0.3Torrで減圧蒸留して、橙色液体を得た。
シュレンクフラスコに、MnCl2(1当量、13g)、1-エチル-3-メチルイミダゾリウムクロライド(2当量)、カリウム2-ブトキシド(4当量)およびTHFを入れて、一晩還流した後、反応を終了させ、室温まで温度を下げて、減圧ろ過して溶媒を除去した。得られた化合物を70℃および0.2Torrで減圧蒸留して、橙色液体を得た。
シュレンクフラスコに、MnCl2(1当量、13g)、1-メチル-3-プロピルイミダゾリウムクロライド(2当量)、カリウム2-ブトキシド(4当量)およびTHFを入れて、室温で一晩撹拌した後、反応を終了させ、減圧ろ過して溶媒を除去した。得られた化合物を65℃および0.2Torrで減圧蒸留して、橙色液体を得た。
シュレンクフラスコに、MnCl2(1当量、3g)、1,3-ジメチルイミダゾリウムクロライド(2当量)、カリウムビス-トリメチルシリルアミド(4当量)およびTHFを入れて、一晩還流した後、反応を終了させ、室温まで温度を下げて、減圧ろ過して溶媒を除去した。得られた化合物を90℃および1Torrで昇華して、黄褐色固体を得た。
シュレンクフラスコに、MnCl2(1当量、3g)、1-エチル-3-メチルイミダゾリウムクロライド(2当量)、カリウムビス-トリメチルシリルアミド(4当量)およびTHFを入れて、一晩還流した後、反応を終了させ、室温まで温度を下げて、減圧ろ過して溶媒を除去した。得られた化合物を80℃および0.4Torrで蒸留して、橙色液体を得た。
シュレンクフラスコに、MnCl2(1当量、3g)、1-メチル-3-プロピルイミダゾリウムクロライド(2当量)、カリウムビス-トリメチルシリルアミド(4当量)およびTHFを入れて、一晩還流した後、反応を終了させ、室温まで温度を下げて、減圧ろ過して溶媒を除去した。得られた化合物を60℃および0.4Torrで蒸留して、橙色液体を得た。
基板上に、実施例1乃至6のいずれか1つの新規マンガン前駆体と酸素(O2)を含む反応ガスを交互に供給してマンガン薄膜を製造した。前駆体と反応ガスを供給した後は、それぞれパージガスであるアルゴンを供給して、蒸着チャンバ内に残存する前駆体と反応ガスをパージした。前駆体の供給時間は8乃至15秒に調節し、反応ガスの供給時間も8乃至15秒に調節した。蒸着チャンバの圧力は1乃至20torrに調節し、蒸着温度は80乃至300℃に調節した。
また、本発明による新規有機金属化合物および前記気相蒸着化合物を含む前駆体組成物は、固体または粘度の低い液体化合物であり、揮発性に優れて均一な薄膜蒸着が可能であり、熱的安定性および反応性が高くて、優れた薄膜物性、厚さおよび段差被覆性の確保が可能である。
上記のような物性は原子層蒸着法および化学気相蒸着法に適した有機金属-含有前駆体を提供し、優れた薄膜特性に寄与する。
Claims (9)
- 下記化学式1で表される、有機金属化合物:
Mは、Mn、Cu、Co、FeまたはNiであり;
aは、2であり;
bは、1または2であり(ただし、MがCoの場合、bは、2ではない);
R1およびR2は、それぞれ独立して、水素、または炭素数1乃至4の線状もしくは分枝状アルキル基であり;
R3は、-OR4または-NR5R6であり;
R4は、水素、または炭素数1乃至4の線状もしくは分枝状アルキル基であり;
R5およびR6は、それぞれ独立して、水素、炭素数1乃至4の線状もしくは分枝状アルキル基、または炭素数1乃至6の線状もしくは分枝状アルキルシリル基である。 - R1、R2、およびR4は、それぞれ独立して、水素、メチル基、エチル基、n-プロピル基、iso-プロピル基、n-ブチル基、iso-ブチル基、sec-ブチル基、およびtert-ブチル基からなる群より選択されるいずれか1つである、請求項1に記載の有機金属化合物。
- R5およびR6は、それぞれ独立して、水素、メチル基、エチル基、n-プロピル基、iso-プロピル基、n-ブチル基、iso-ブチル基、sec-ブチル基、tert-ブチル基、メチルシリル基、ジメチルシリル基、トリメチルシリル基、およびトリエチルシリル基からなる群より選択されるいずれか1つである、請求項1に記載の有機金属化合物。
- 請求項1乃至請求項3のいずれか1項に記載の有機金属化合物を含む、気相蒸着用前駆体組成物。
- 請求項4に記載の気相蒸着用前駆体組成物をチャンバに導入するステップを含む、薄膜の製造方法。
- 前記薄膜の製造方法は、原子層蒸着法(ALD)または化学気相蒸着法(CVD)を含む、請求項5に記載の薄膜の製造方法。
- 反応ガスとして、水素(H2)、酸素(O)原子含有化合物、窒素(N)原子含有化合物またはケイ素(Si)原子含有化合物の中から選択されたいずれか1つ以上を注入するステップをさらに含む、請求項5に記載の薄膜の製造方法。
- 前記反応ガスは、水(H2O)、酸素(O2)、水素(H2)、オゾン(O3)、アンモニア(NH3)、ヒドラジン(N2H4)またはシラン(Silane)の中から選択
されたいずれか1つ以上である、請求項7に記載の薄膜の製造方法。 - 請求項4に記載の気相蒸着用前駆体組成物を用いて製造された、有機金属含有薄膜。
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