WO2024128535A1 - Gallium compound, composition for thin film deposition, comprising same, and thin film manufacturing method using same - Google Patents
Gallium compound, composition for thin film deposition, comprising same, and thin film manufacturing method using same Download PDFInfo
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- WO2024128535A1 WO2024128535A1 PCT/KR2023/017095 KR2023017095W WO2024128535A1 WO 2024128535 A1 WO2024128535 A1 WO 2024128535A1 KR 2023017095 W KR2023017095 W KR 2023017095W WO 2024128535 A1 WO2024128535 A1 WO 2024128535A1
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- Prior art keywords
- gallium
- thin film
- formula
- compound
- alkyl
- Prior art date
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- 150000002259 gallium compounds Chemical class 0.000 title claims abstract description 87
- 239000010409 thin film Substances 0.000 title claims abstract description 86
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 37
- 239000000203 mixture Substances 0.000 title claims abstract description 18
- 238000000427 thin-film deposition Methods 0.000 title claims abstract description 16
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 83
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 73
- 239000002243 precursor Substances 0.000 claims abstract description 49
- 239000000758 substrate Substances 0.000 claims abstract description 24
- -1 allylamine compound Chemical class 0.000 claims description 65
- 238000000034 method Methods 0.000 claims description 31
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 28
- 238000000231 atomic layer deposition Methods 0.000 claims description 22
- 238000000151 deposition Methods 0.000 claims description 22
- 229910052738 indium Inorganic materials 0.000 claims description 16
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 15
- 238000005229 chemical vapour deposition Methods 0.000 claims description 12
- 229910052725 zinc Inorganic materials 0.000 claims description 12
- 239000011701 zinc Substances 0.000 claims description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 11
- 125000006374 C2-C10 alkenyl group Chemical group 0.000 claims description 10
- VVJKKWFAADXIJK-UHFFFAOYSA-N allylamine Natural products NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 10
- 230000008021 deposition Effects 0.000 claims description 10
- 229910052736 halogen Inorganic materials 0.000 claims description 10
- 150000002367 halogens Chemical class 0.000 claims description 10
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 9
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 7
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 claims description 6
- 239000011787 zinc oxide Substances 0.000 claims description 6
- 229910001195 gallium oxide Inorganic materials 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- 229910002601 GaN Inorganic materials 0.000 claims description 3
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 21
- 239000010408 film Substances 0.000 description 14
- 125000004432 carbon atom Chemical group C* 0.000 description 12
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 229940125904 compound 1 Drugs 0.000 description 10
- 238000010926 purge Methods 0.000 description 10
- 239000004065 semiconductor Substances 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- 238000002347 injection Methods 0.000 description 9
- 239000007924 injection Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 7
- 239000012495 reaction gas Substances 0.000 description 7
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 238000006138 lithiation reaction Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000002411 thermogravimetry Methods 0.000 description 4
- IBEFSUTVZWZJEL-UHFFFAOYSA-N trimethylindium Chemical compound C[In](C)C IBEFSUTVZWZJEL-UHFFFAOYSA-N 0.000 description 4
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 239000007806 chemical reaction intermediate Substances 0.000 description 3
- OWQWEJKPOUNPPG-UHFFFAOYSA-M chloro(dimethyl)gallane Chemical compound C[Ga](C)Cl OWQWEJKPOUNPPG-UHFFFAOYSA-M 0.000 description 3
- 238000000113 differential scanning calorimetry Methods 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910021482 group 13 metal Inorganic materials 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 239000012705 liquid precursor Substances 0.000 description 3
- 238000004518 low pressure chemical vapour deposition Methods 0.000 description 3
- DYUWTXWIYMHBQS-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCNCC=C DYUWTXWIYMHBQS-UHFFFAOYSA-N 0.000 description 3
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 2
- 125000005916 2-methylpentyl group Chemical group 0.000 description 2
- 125000003469 3-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000005917 3-methylpentyl group Chemical group 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000014509 gene expression Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 2
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- XCZXGTMEAKBVPV-UHFFFAOYSA-N trimethylgallium Chemical compound C[Ga](C)C XCZXGTMEAKBVPV-UHFFFAOYSA-N 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DIIIISSCIXVANO-UHFFFAOYSA-N 1,2-Dimethylhydrazine Chemical compound CNNC DIIIISSCIXVANO-UHFFFAOYSA-N 0.000 description 1
- 125000004973 1-butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000006039 1-hexenyl group Chemical group 0.000 description 1
- 125000006023 1-pentenyl group Chemical group 0.000 description 1
- 125000003562 2,2-dimethylpentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000006069 2,3-dimethyl-2-butenyl group Chemical group 0.000 description 1
- 125000003660 2,3-dimethylpentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000003764 2,4-dimethylpentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 1
- 125000006040 2-hexenyl group Chemical group 0.000 description 1
- 125000006029 2-methyl-2-butenyl group Chemical group 0.000 description 1
- 125000006024 2-pentenyl group Chemical group 0.000 description 1
- 125000006325 2-propenyl amino group Chemical class [H]C([H])=C([H])C([H])([H])N([H])* 0.000 description 1
- 125000004336 3,3-dimethylpentyl group Chemical group [H]C([H])([H])C([H])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- HZVMDZFIUJZIOT-UHFFFAOYSA-N 3-dimethylindiganyl-n,n-dimethylpropan-1-amine Chemical compound CN(C)CCC[In](C)C HZVMDZFIUJZIOT-UHFFFAOYSA-N 0.000 description 1
- 125000004337 3-ethylpentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000006041 3-hexenyl group Chemical group 0.000 description 1
- 125000006027 3-methyl-1-butenyl group Chemical group 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910005540 GaP Inorganic materials 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- 229910000673 Indium arsenide Inorganic materials 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229910003811 SiGeC Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910000577 Silicon-germanium Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- NTYDXFVCCCPXRG-UHFFFAOYSA-N [Li]C(C)(C)CC(C)(C)C Chemical compound [Li]C(C)(C)CC(C)(C)C NTYDXFVCCCPXRG-UHFFFAOYSA-N 0.000 description 1
- SHJXVDAAVHAKFB-UHFFFAOYSA-N [Li]CCCCCCCCCC Chemical compound [Li]CCCCCCCCCC SHJXVDAAVHAKFB-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910000085 borane Inorganic materials 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
- 239000006227 byproduct Substances 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
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- 238000002485 combustion reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- ZOCHARZZJNPSEU-UHFFFAOYSA-N diboron Chemical compound B#B ZOCHARZZJNPSEU-UHFFFAOYSA-N 0.000 description 1
- ZZEMEJKDTZOXOI-UHFFFAOYSA-N digallium;selenium(2-) Chemical compound [Ga+3].[Ga+3].[Se-2].[Se-2].[Se-2] ZZEMEJKDTZOXOI-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- SZEJQLSRYARYHS-UHFFFAOYSA-N dimethylindium Chemical compound C[In]C SZEJQLSRYARYHS-UHFFFAOYSA-N 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- BLHLJVCOVBYQQS-UHFFFAOYSA-N ethyllithium Chemical compound [Li]CC BLHLJVCOVBYQQS-UHFFFAOYSA-N 0.000 description 1
- LJJVZJSGXHJIPP-UHFFFAOYSA-N ethylpentyl Chemical group [CH2+]CCC[CH]C[CH2-] LJJVZJSGXHJIPP-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229920002457 flexible plastic Polymers 0.000 description 1
- 150000002258 gallium Chemical class 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- RPQDHPTXJYYUPQ-UHFFFAOYSA-N indium arsenide Chemical compound [In]#[As] RPQDHPTXJYYUPQ-UHFFFAOYSA-N 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
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- SZAVVKVUMPLRRS-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].C[CH-]C SZAVVKVUMPLRRS-UHFFFAOYSA-N 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 1
- 229910003465 moissanite Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- IOXXVNYDGIXMIP-UHFFFAOYSA-N n-methylprop-2-en-1-amine Chemical compound CNCC=C IOXXVNYDGIXMIP-UHFFFAOYSA-N 0.000 description 1
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- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
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- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
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- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
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- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
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- 238000003756 stirring Methods 0.000 description 1
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- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Images
Classifications
-
- 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
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
- C23C16/18—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metallo-organic compounds
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/34—Nitrides
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—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
- C23C16/44—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
Definitions
- the present invention relates to a gallium compound, a method for producing the same, a composition for thin film deposition containing the same, and a method for producing a thin film using the same. More specifically, a gallium compound useful as a precursor for depositing a gallium-containing thin film, a method for producing the same, and a composition containing the same. It relates to a composition for depositing a gallium-containing thin film and a method of manufacturing a gallium-containing thin film using the same.
- the development of new technologies and materials in the semiconductor industry has made possible miniaturization, high reliability, high speed, high functionality, and high integration of devices such as semiconductor integrated circuits. Accordingly, the properties required for precursors to form thin films have also changed.
- the characteristics required for a thin film deposition precursor are a gas or liquid compound with high vapor pressure, excellent thermal stability, and easy transfer to the deposition chamber, and furthermore, reactivity with the reaction gases used depending on the type of thin film being manufactured. must also be excellent.
- PVD method physical vapor growth method
- CVD method chemical vapor growth method
- precursors containing Group 13 metals have excellent stability and conductivity, and are attracting attention as precursors for thin film deposition.
- group 13 metal oxides can be used as transparent oxide semiconductor materials and can be applied as electrodes, conductive coating materials, etc.
- Gallium oxide which contains gallium among group 13 metals, has a wide band gap energy and is used in display fields such as gas sensors and transparent conductors, as well as next-generation solar cells, specifically phosphor raw materials, semiconductors, and CIGS (copper).
- indium gallium selenide It is used as a material applicable to solar cells, ultra-thin liquid crystal displays (TFT-LCD), and organic light-emitting diodes (OLED).
- gallium oxide is an electrical insulator at room temperature and a semiconductor at temperatures above 500°C, having a chemically and thermally stable monoclinic form.
- Trimethylgallium is the most widely used gallium precursor, but it is very sensitive to air and ignites spontaneously when exposed, making it difficult to handle.
- Gallium fluoride (GaF) is formed due to fluorine, causing contamination in the thin film, which can cause serious deterioration of device characteristics and reliability problems during the semiconductor device process.
- gallium alkoxide dimers or tetramers were reported, but they did not correspond to a single monomer and had low volatility to be used as a precursor for thin film deposition.
- Precursors for thin film deposition necessarily require high volatility and thermal stability, but previously reported gallium compounds have insufficient volatility to be used as precursors or have problems of contaminating thin films with halogen elements, including halogen elements. .
- the compound itself does not contain halogen elements such as fluorine, but contains gallium that can be applied to ALD and CVD processes with high volatility and thermal stability. There is a need for the development of precursors for thin film deposition.
- the present invention provides a gallium compound that has improved volatility and thermal stability and is very useful for producing high-quality gallium-containing thin films, and a method for producing the same.
- the present invention provides a composition for depositing a gallium-containing thin film containing the gallium compound of the present invention.
- the present invention provides a method for producing a gallium-containing thin film using the gallium compound or the composition for depositing a gallium-containing thin film of the present invention.
- One aspect of the present invention is to provide a gallium compound that is very useful as a precursor for gallium-containing thin films due to its excellent volatility and stability.
- the gallium compound of the present invention is represented by the following formula (1).
- R 1 and R 2 are independently C1-C10 alkyl or ego;
- R 3 and R' are independently C1-C10 alkyl or C2-C10 alkenyl.
- Another aspect of the present invention is to provide a method for producing the gallium compound.
- the method for producing the gallium compound of the present invention is to lithium an allylamine compound of the following formula (4) and then reacting with a dialkyl gallium halide compound of the formula (5). It includes preparing a gallium compound of Formula 1-1.
- R 2a is C1-C10 alkyl
- R 1a is C1-C10 alkyl
- R 3 and R' are independently C1-C10 alkyl or C2-C10 alkenyl
- hal is halogen
- Another aspect of the present invention is to provide a method for producing the gallium compound.
- the method for producing the gallium compound of the present invention is to lithium an allylamine compound of the following formula (4) and then reacting with an alkyl gallium dihalide compound of the formula (6) to produce It includes preparing a gallium compound of Formula 1-2.
- R 2a is C1-C10 alkyl
- R 3 and R' are independently C1-C10 alkyl or C2-C10 alkenyl
- hal is halogen
- Another aspect of the present invention provides a composition for depositing a gallium-containing thin film containing a gallium compound represented by Formula 1 according to an embodiment, and a method of forming a gallium-containing thin film using the same.
- Another aspect of the present invention provides a method of forming a gallium-containing thin film using a gallium compound represented by Formula 1 according to an embodiment.
- the gallium compound of the present invention has good thermal stability, high volatility, and excellent cohesiveness, so it is useful as a precursor for gallium-containing thin films. Furthermore, it has excellent adsorption with a substrate, making it possible to produce higher quality gallium-containing thin films.
- the gallium compound of the present invention exists in a solid or liquid state at room temperature and a manageable pressure, making it easy to handle.
- the gallium compound of the present invention exists in a solid or liquid state at room temperature, it is supplied at a uniform concentration to a large-area substrate and has excellent thin film thickness uniformity. Additionally, the gallium compound of the present invention does not decompose even during high processing temperatures and does not decompose. , Excellent storage stability.
- the method for manufacturing a gallium-containing thin film of the present invention enables the production of a high-quality gallium-containing thin film with excellent thermal stability and durability by manufacturing a gallium-containing thin film using the gallium compound or a composition for gallium-containing thin film deposition containing the gallium compound. .
- thermal stability may mean that physical properties do not change even during a continuous heating process or a high temperature process, and specifically means that no structural change occurs even when exposed to the harsh conditions described above for a long period of time. .
- alkyl refers to a saturated straight-chain or branched non-cyclic hydrocarbon having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, and more preferably 1 to 4 carbon atoms. “Lower alkyl” means straight-chain or branched alkyl having 1 to 4 carbon atoms.
- saturated straight-chain alkyls include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl and n-decyl, while saturated branched alkyls include Alkyl is isopropyl, sec-butyl, isobutyl, tert-butyl, isopentyl, 2-methylhexyl, 3-methylbutyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2-methylhexyl, 3 -Methylhexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 2,3-dimethylbutyl, 2,3- Dimethylpentyl, 2,4-di
- C1-C10 When written as “C1-C10” in this specification, it means that the number of carbon atoms is 1 to 10.
- C1-C4alkyl refers to alkyl having 1 to 4 carbon atoms. Specific examples may be methyl, ethyl, propyl, iso-propyl, butyl, iso-butyl, or tert-butyl. .
- alkenyl refers to a saturated straight-chain or branched group containing 2 to 10 carbon atoms, preferably 2 to 6 carbon atoms, more preferably 2 to 4 carbon atoms and at least one carbon-carbon double bond. refers to terrestrial non-cyclic hydrocarbons.
- Representative straight-chain and branched (C2-C10) alkenyls include vinyl, allyl, 1-butenyl, 2-butenyl, isobutenyl, 1-pentenyl, 2-pentenyl, 3-methyl-1-butenyl, 2-methyl-2-butenyl, 2,3-dimethyl-2-butenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 1-heptenyl, 2-heptenyl, 3- Heptenyl, 1-octenyl, 2-octenyl, 3-octenyl, 1-nonenyl, 2-nonenyl, 3-nonenyl, 1-decenyl, 2-decenyl, and 3-decenyl Includes. These alkenyl groups may be optionally substituted.
- One aspect of the present invention is to provide a gallium compound that can be very useful as a precursor for a gallium-containing thin film.
- the gallium compound of the present invention is represented by the following formula (1).
- R 1 and R 2 are independently C1-C10 alkyl or ego;
- R 3 and R' are independently C1-C10 alkyl or C2-C10 alkenyl.
- R 2 may be C1-C10 alkyl, C1-C6 alkyl, or C1-C4 alkyl.
- R 1 , R 2 and R 3 may independently be C1-C10 alkyl, C1-C6 alkyl, or C1-C4 alkyl.
- R 1 , R 2 and R 3 may each independently be methyl or ethyl.
- R 1 and R 2 may each independently be C1-C10 alkyl, and R 3 may be allyl.
- the gallium compound may be represented by the following formula (2).
- R 1 and R 2 are independently C1-C4 alkyl.
- R 1 and R 2 may independently be methyl, ethyl, isopropyl, or t-butyl.
- R 1 is , R' may be C1-C10 alkyl or allyl, R 2 may be C1-C10 alkyl, and R 3 may be C1-C10 alkyl or allyl.
- the gallium compound may be represented by the following formula (3).
- R 2 is C1-C4alkyl
- R'' is C1-C4alkyl or allyl.
- R 2 may be methyl or ethyl
- R'' may be methyl, ethyl, isopropyl, or allyl.
- the gallium compound of the present invention has a structure in which an alkylylamino ligand or diallylamino ligand is bonded to the central metal gallium (Ga). Due to the introduction of this allylamino ligand, thermal stability and reactivity are significantly improved and at the same time, it is highly volatile. High-quality thin films can be manufactured.
- the gallium compound of the present invention exists in solid or liquid form at room temperature and pressure, it has high storage stability and excellent volatility, so it can be used as a precursor for deposition of gallium-containing thin films to produce high-density, high-purity gallium-containing thin films. .
- liquid precursors In atomic layer deposition (ALD), the reactants must be highly volatile, the material must be stable, and the reactivity must be high. Accordingly, most semiconductor manufacturers (chip makers) prefer liquid precursors due to their advantages in the process. However, despite these advantages, solid precursors are still used because they are cheaper than liquid precursors and have fewer disadvantages than liquid precursors, such as unreliability due to severe contamination of thin films due to unstable decomposition or low reactivity during the process. am.
- Another aspect of the present invention is to provide a method for producing the gallium compound.
- a method for producing a gallium compound according to an embodiment includes preparing a gallium compound of the formula 1-1 by lithiuming an allylamine compound of the formula 4 below and then reacting it with a dialkyl gallium halide compound of the formula 5 below. .
- R 2a is C1-C10 alkyl
- R 1a is C1-C10 alkyl
- R 3 and R' are independently C1-C10 alkyl or C2-C10 alkenyl
- hal is halogen
- a method for producing a gallium compound according to an embodiment includes preparing a gallium compound of the formula 1-2 by lithiuming an allylamine compound of the formula 4 below and reacting it with an alkylgallium dihalide compound of the formula 6 below. .
- R 2a is C1-C10 alkyl
- R 3 and R' are independently C1-C10 alkyl or C2-C10 alkenyl
- hal is halogen
- the method for producing a gallium compound according to an embodiment may be, for example, produced by the same method as described above, but any other method is possible within the range recognized by a person skilled in the art.
- the lithiation is a step of reacting the allylamine compound of Formula 4 with alkyl lithium having 1 to 10 carbon atoms
- alkyl lithium compounds that can be commonly used for lithiation of organic compounds can be used without limitation.
- the alkyl lithium having 1 to 10 carbon atoms is selected from the group consisting of methyl lithium, ethyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, n-decyl lithium and tert-octyl lithium.
- n-butyllithium, sec-butyllithium, tert-butyllithium, etc. can be preferably used.
- the allylamine compound of Formula 4 is cooled to less than 10°C, preferably to 10 to -10°C, a solvent is added, and then alkyllithium having 1 to 10 carbon atoms is added, and then the above-mentioned amine compound is measured through NMR measurement.
- Lithiumization can be performed by stirring at 10 to 30° C., or 20 to 25° C., until the NH peak of the allylamine compound of Formula 4 disappears.
- the desired gallium compound (Formula 1-1 or Formula 1-2) is obtained by metallization with the reaction intermediate that has undergone the above-described lithiation step and the dialkyl gallium halide compound of Formula 5 or the alkyl gallium dihalide compound of Formula 6. can be obtained.
- the reaction intermediate that has undergone the lithiation step is cooled to less than 10° C., preferably 10 to -10° C., and then the dialkyl gallium halide compound of Formula 5 or the alkyl gallium dihalide compound of Formula 6 is added to hexane, etc. is dispersed or dissolved in an organic solvent and slowly injected into the cooled reaction intermediate, and then stirred at 10 to 30° C., or 20 to 25° C. for 5 hours or more, or 10 hours or more, preferably 15 to 20 hours, to metallize.
- the reaction can be carried out.
- the reaction may be performed under an inert gas atmosphere such as nitrogen or argon.
- Another aspect of the present invention provides a composition for depositing a gallium-containing thin film containing a gallium compound represented by Formula 1 according to an embodiment, and a method of forming a gallium-containing thin film using the same.
- composition for thin film deposition may be specifically for indium gallium zinc oxide (IGZO) thin film deposition.
- IGZO indium gallium zinc oxide
- gallium compounds described above it may further include an indium precursor and a zinc precursor.
- the indium precursor may be C1-C6 alkyl indium
- the zinc precursor may be C1-C6 alkyl zinc.
- the indium precursor may be trimethylindium (TMI) or dimethylaminopropyldimethylindium (3-(Dimethylamino)propryl). (dimethyl)indium; DADI), and the zinc precursor may be diethylzinc (DEZ), but is not limited thereto.
- the molar ratio of the indium precursor: gallium precursor: zinc precursor may be 1 to 10:1 to 10:1 to 10, specifically 1 to 5:1 to 5:1 to 5, more specifically 1:1:1. You can.
- Another aspect of the present invention provides a method of forming a gallium-containing thin film using a gallium compound represented by Formula 1 according to an embodiment.
- the method for manufacturing the indium-containing thin film according to an embodiment may be atomic layer deposition (ALD), chemical vapor deposition (CVD), or metal organic chemical vapor deposition (MOCVD).
- ALD atomic layer deposition
- CVD chemical vapor deposition
- MOCVD metal organic chemical vapor deposition
- a gallium-containing thin film according to an embodiment may be manufactured by a common method used in the art, for example, metal organic chemical vapor deposition (MOCVD), atomic layer deposition (ALD), low pressure vapor deposition (LPCVD), and plasma enhanced Examples include vapor deposition (PECVD) or plasma enhanced atomic layer deposition (PEALD), but atomic layer deposition (ALD) or plasma enhanced atomic layer deposition (PEALD) is preferred.
- MOCVD metal organic chemical vapor deposition
- ALD atomic layer deposition
- LPCVD low pressure vapor deposition
- PECVD plasma enhanced atomic layer deposition
- PEALD plasma enhanced atomic layer deposition
- PEALD plasma enhanced atomic layer deposition
- the gallium-containing thin film of the present invention may be manufactured by atomic layer deposition (ALD).
- ALD atomic layer deposition
- a method of manufacturing a gallium-containing thin film may include forming a single-layer or multi-layer thin film by depositing the gallium compound and at least one selected from an indium precursor and a zinc precursor on a substrate, wherein the gallium compound, The indium precursor and the zinc precursor can be deposited on the substrate simultaneously, or the gallium compound, the indium precursor, and the zinc precursor can be mixed and deposited on the substrate to form a thin film with a single-layer structure, and the indium precursor, the gallium compound, and the zinc precursor can be deposited on the substrate. may be sequentially deposited on a substrate to form a thin film with a multilayer structure.
- the indium precursor may be trimethylindium (TMI), and the zinc precursor may be diethylzinc (DEZ), but are not limited thereto.
- the multilayer thin film may be an indium-gallium-zinc oxide film (IGZO thin film), and the composition ratio of indium:gallium:zinc may be 1 to 10:1 to 10:1 to 10, specifically 1 to 5:1. to 5:1 to 5, more specifically 1:1:1.
- the gallium-containing thin film according to one embodiment is manufactured using the gallium compound, and is not limited, but is preferably a gallium nitride film, a gallium oxide film, or an indium-gallium-zinc oxide film, and is preferably a gallium oxide film or an indium-gallium-zinc oxide film. It may be a zinc oxide film.
- the injection temperature of the gallium compound of the present invention may be room temperature (25°C to 120°C, and due to the high volatility of the gallium compound of the present invention, the temperature of the substrate on which the gallium compound will be deposited is 100 to 450°C, and the pressure inside the chamber may be 0.1 to 10 torr.
- the reaction gas used in the method for manufacturing a gallium-containing thin film according to an embodiment is not limited, but includes hydrogen (H 2 ), hydrazine (N 2 H 4 ), dimethylhydrazine (Me 2 N 2 H 2 ), and ozone ( O 3 ), oxygen (O 2 ), water (H 2 O), ammonia (NH 3 ), nitrogen (N 2 ), silane (SiH 4 ), borane (BH 3 ), diborane (B 2 H 6 ), and
- One or more mixed gases selected from phosphine (PH 3 ) can be used, and the reaction gas is not limited, but can be supplied at a flow rate of 10 to 10,000 sccm, specifically 50 to 1,000 sccm. It can be.
- oxidizing reaction gases such as water vapor (H 2 O), oxygen (O 2 ), or ozone (O 3 )
- a gallium oxide film may be formed, and ammonia (NH 3 ) or hydrazine (N 2 H 4 )
- a nitrogen-containing reaction gas such as, a gallium nitride film may be formed.
- the purge gas is an inert gas, but is not limited thereto, and may be one or a mixture of two or more gases selected from argon (Ar) and helium (He).
- the substrate used in the method of manufacturing a gallium-containing thin film includes a substrate containing one or more semiconductor materials selected from the group consisting of Si, SiO2, Pt, TiN, Ge, SiGe, GaP, GaAs, SiC, SiGeC, InAs, and InP; SOI (Silicon On Insulator) substrate; Quartz substrate; or a glass substrate for display; Polyimide, PolyEthylene Terephthalate (PET), PolyEthylene Naphthalate (PEN), Poly Methyl MethAcrylate (PMMA), Polycarbonate (PC, PolyCarbonate), Polyether Sulfone Flexible plastic substrates such as (PES) and polyester; It may be, but is not limited to this.
- the method for manufacturing a gallium-containing thin film according to an embodiment has high volatility and high thermal stability, and by using it as a precursor for thin film deposition, the gallium-containing thin film has excellent physical, electrical and chemical properties, and has high density and high purity, and is of good quality and uniformity. can be formed.
- the synthesis of the gallium compound according to the present invention was performed using a standard Schlenk flask or purge box under an inert argon or nitrogen atmosphere, except where otherwise noted.
- the structure of the obtained gallium compound was analyzed through 1 H NMR spectrum and elemental analysis.
- the thickness of the deposited gallium-containing thin film was measured using an ellipsometer (Ellipsometer, Thermowave, Optiprobe 2600) and X-ray photoelectron spectroscopy (XPS, X-ray Photoelectron Spectroscopy, ThermoFisher Scientific, K-Alpha+).
- the composition of the thin film was analyzed.
- a 250ml Schlenk flask and two 100ml Schlenk flasks dried in an oven were placed in a purge box and purged for more than 30 minutes to remove as much moisture inside the glassware as possible.
- thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) were used (measurement conditions: 500°C at 10Kmin -1 under a nitrogen atmosphere. (temperature increased to °C).
- Gallium Compound 1 prepared in Example 1 was used as a precursor for deposition of gallium-containing thin films, ozone (O 3 ) was used as a reaction gas, the concentration of ozone was 220 g/m3, and argon ( A gallium-containing thin film was formed by atomic layer deposition (ALD) using Ar).
- ozone O 3
- argon A gallium-containing thin film was formed by atomic layer deposition (ALD) using Ar).
- a silicon oxide film was used as a substrate.
- a silicon oxide film substrate was loaded inside the deposition chamber, and the substrate temperature was set to 250°C.
- gallium compound 1 was placed in a stainless steel bubbler and maintained at 30°C.
- Thin film deposition using a gallium precursor was performed by repeating 100 cycles of four sequential steps: gallium precursor injection - purge (Ar) - ozone (O 3 ) injection - purge (Ar) to deposit a gallium-containing thin film.
- Table 1 shows detailed deposition conditions and results.
- the growth rate per cycle (GPC) according to the injection time of gallium compound 1 was measured and shown in FIG. 3. From Table 1 and Figure 3, the GPC of the gallium precursor according to the present invention increases from 1 to 3 seconds of injection time, and the GPC is maintained at a constant level from 3 seconds of injection time, resulting in saturation from 3 seconds of injection time of the gallium precursor. It was confirmed that the growth rate of the gallium-containing thin film was constant.
- the gallium compound according to the present invention has excellent thermal stability and volatility and is useful as a precursor for gallium-containing thin films. It has a high vapor pressure, enabling uniform thin film deposition through uniform composition control through uniform precursor supply during thin film production. High-density and high-purity gallium-containing thin films can be easily manufactured.
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Abstract
The present invention relates to a gallium compound, a preparation method therefor, a composition for thin film deposition, comprising same, and a thin film manufacturing method using same, the gallium compound of the present invention having excellent volatility and stability, thereby being very useful as a precursor for a gallium-containing thin film, and having excellent adsorption to a substrate, thereby enabling the manufacturing of a higher-quality gallium-containing thin film.
Description
본 발명은 갈륨 화합물, 이의 제조방법, 이를 포함하는 박막 증착용 조성물 및 이를 이용한 박막의 제조 방법에 관한 것으로, 보다 상세하게는 갈륨 함유 박막 증착용 전구체로 유용한 갈륨 화합물, 이의 제조방법, 이를 포함하는 갈륨 함유 박막 증착용 조성물 및 이를 이용한 갈륨 함유 박막의 제조 방법에 관한 것이다.The present invention relates to a gallium compound, a method for producing the same, a composition for thin film deposition containing the same, and a method for producing a thin film using the same. More specifically, a gallium compound useful as a precursor for depositing a gallium-containing thin film, a method for producing the same, and a composition containing the same. It relates to a composition for depositing a gallium-containing thin film and a method of manufacturing a gallium-containing thin film using the same.
반도체 산업에서의 신기술 및 재료의 개발로 인해 반도체 집적회로와 같은 소자의 미세화, 고신뢰화, 고속화, 고기능화, 고집적화 등이 가능해졌다. 이에 따라 박막을 형성하기 위한 전구체에 요구되는 특성도 변화되어 왔다. 일반적으로 박막증착용 전구체에 요구되는 특성은 증기압이 높고 열 안정성이 우수하며 증착 챔버로의 이송이 쉬운 기체 또는 액체상의 화합물이어야 하고, 나아가 제조되는 박막의 종류에 따라 사용되는 반응 가스들과의 반응성도 우수해야 한다.The development of new technologies and materials in the semiconductor industry has made possible miniaturization, high reliability, high speed, high functionality, and high integration of devices such as semiconductor integrated circuits. Accordingly, the properties required for precursors to form thin films have also changed. In general, the characteristics required for a thin film deposition precursor are a gas or liquid compound with high vapor pressure, excellent thermal stability, and easy transfer to the deposition chamber, and furthermore, reactivity with the reaction gases used depending on the type of thin film being manufactured. must also be excellent.
또한 반도체용 소자 제조에 이용되고 있는 박막의 형성방법으로서는, 스퍼터링에 의한 물리기상성장법(PVD법) 및 화학기상성장법(CVD법)을 들 수 있다. 그러나 차세대 이후의 반도체 제조에서는, 미세화한 소자의 복잡한 3차원 구조의 표면에도 균일한 박막이 요구됨에 따라, 요철이 있는 면에 균일한 막을 형성하는 것이 어려운 PVD법은 적절하지는 않다.Additionally, thin film formation methods used in the manufacture of semiconductor devices include physical vapor growth method (PVD method) and chemical vapor growth method (CVD method) by sputtering. However, in the next generation of semiconductor manufacturing, a uniform thin film is required even on the surface of a complex three-dimensional structure of a miniaturized device, so the PVD method is not suitable because it is difficult to form a uniform film on the uneven surface.
이에 따라, 단차 피복성이 우수한 박막을 형성하는 방법으로, 원료를 기체로서 반응조로 이송시키고, 분해시켜 막을 형성시키는 CVD법 또는 기판 표면에 흡착시킨 원료를 분해시켜 막을 퇴적시키는 원자층 증착법(ALD법)에 의한 박막 형성법이 검토되고 주로 사용되고 있다.Accordingly, as a method of forming a thin film with excellent step coverage, a CVD method in which raw materials are transferred to a reaction tank as a gas and decomposed to form a film, or an atomic layer deposition (ALD) method in which raw materials adsorbed on the substrate surface are decomposed and a film is deposited ) Thin film formation method has been reviewed and is mainly used.
한편 13족 금속을 포함하는 전구체는 우수한 안정성 및 전도성을 가지는 전구체로서, 박막 증착을 위한 전구체로서 각광을 받고 있다. 특히, 13족 금속 산화물은 투명 산화물 반도체 소재로 사용 가능하며 전극, 전도성 코팅재료 등으로 응용이 가능하다.Meanwhile, precursors containing Group 13 metals have excellent stability and conductivity, and are attracting attention as precursors for thin film deposition. In particular, group 13 metal oxides can be used as transparent oxide semiconductor materials and can be applied as electrodes, conductive coating materials, etc.
13족 금속 중 갈륨을 함유하는 산화갈륨(gallium oxide, Ga2O3)은 밴드 갭 에너지가 넓어 가스 센서 및 투과성 전도체 등의 디스플레이 분야 및 차세대 태양전지, 구체적으로, 형광체 원료, 반도체, CIGS(copper indium gallium selenide) 태양전지, 초박막액정표시장치(TFT-LCD), 유기발광다이오드(OLED) 등에 적용 가능한 재료로 사용되고 있다. 또한, 산화갈륨은 상온에서는 전기 절연체(electrical insulator)이고, 화학적, 열적으로 안정한 단사결정계 형태(monoclinic form)를 갖는 500 ℃ 이상의 온도에서는 반도체(semiconducting)이다.Gallium oxide (Ga 2 O 3 ), which contains gallium among group 13 metals, has a wide band gap energy and is used in display fields such as gas sensors and transparent conductors, as well as next-generation solar cells, specifically phosphor raw materials, semiconductors, and CIGS (copper). indium gallium selenide) It is used as a material applicable to solar cells, ultra-thin liquid crystal displays (TFT-LCD), and organic light-emitting diodes (OLED). In addition, gallium oxide is an electrical insulator at room temperature and a semiconductor at temperatures above 500°C, having a chemically and thermally stable monoclinic form.
갈륨 전구체로는 트리메틸갈륨(trimethylgallium, TMG)이 가장 널리 사용되고 있으나, 이는 공기 중에 매우 민감하여 노출되었을 때 자연 발화되므로 취급이 용이하지 않았다. 그 외 [Ga(hfac)]3 (hfac = hexafluoroacetylacetonate) 및 [Ga(OCH(CF3)2)3(HNMe2)] 등의 갈륨 착화합물이 보고 되었으나, 이는 할로겐 원소, 특히 불소를 포함하고 있어 박막 증착시 불소로 인해 불화갈륨(GaF)이 형성되어 박막에 오염을 발생시켜, 반도체 소자 공정 중에 심각한 소자 특성 저하 및 신뢰도 문제를 야기할 수 있다. 또한, 갈륨 알콕사이드 이량체 또는 사량체가 보고되었으나, 이는 단일 단위체에 해당되지 않아 박막 증착을 위한 전구체로 사용하기에 낮은 휘발성을 가졌다.Trimethylgallium (TMG) is the most widely used gallium precursor, but it is very sensitive to air and ignites spontaneously when exposed, making it difficult to handle. In addition, gallium complexes such as [Ga(hfac)]3 (hfac = hexafluoroacetylacetonate) and [Ga(OCH(CF3)2)3(HNMe2)] have been reported, but they contain halogen elements, especially fluorine, so they are difficult to deposit when depositing thin films. Gallium fluoride (GaF) is formed due to fluorine, causing contamination in the thin film, which can cause serious deterioration of device characteristics and reliability problems during the semiconductor device process. In addition, gallium alkoxide dimers or tetramers were reported, but they did not correspond to a single monomer and had low volatility to be used as a precursor for thin film deposition.
박막증착용 전구체는 높은 휘발성과 열안정성이 필수적으로 요구되나, 기보고된 갈륨 화합물들은 전구체로 사용하기에는 충분치 못한 휘발성을 갖거나, 할로겐 원소를 포함하여 할로겐 원소에 의해 박막을 오염시키는 문제점을 가지고 있다.Precursors for thin film deposition necessarily require high volatility and thermal stability, but previously reported gallium compounds have insufficient volatility to be used as precursors or have problems of contaminating thin films with halogen elements, including halogen elements. .
따라서, 수분이나 공기 중에서 반응성이 적어 자연발화의 우려가 없고 취급이 용이하며, 화합물 자체에 불소와 같은 할로겐 원소를 포함하지 않으면서, 높은 휘발성과 열안정성을 갖는 ALD 및 CVD 공정에 적용 가능한 갈륨 함유 박막증착용 전구체의 개발이 요구되고 있다.Therefore, it is less reactive in moisture or air, so there is no risk of spontaneous combustion and is easy to handle. The compound itself does not contain halogen elements such as fluorine, but contains gallium that can be applied to ALD and CVD processes with high volatility and thermal stability. There is a need for the development of precursors for thin film deposition.
본 발명은 향상된 휘발성 및 열안정성을 가져 양질의 갈륨 함유 박막의 제조에 매우 유용한 갈륨 화합물 및 이의 제조방법을 제공한다.The present invention provides a gallium compound that has improved volatility and thermal stability and is very useful for producing high-quality gallium-containing thin films, and a method for producing the same.
또한 본 발명은 본 발명의 갈륨 화합물을 포함하는 갈륨 함유 박막 증착용 조성물을 제공한다.Additionally, the present invention provides a composition for depositing a gallium-containing thin film containing the gallium compound of the present invention.
또한 본 발명은 본 발명의 갈륨 화합물 또는 갈륨 함유 박막 증착용 조성물을 이용하는 갈륨 함유 박막의 제조방법을 제공한다.Additionally, the present invention provides a method for producing a gallium-containing thin film using the gallium compound or the composition for depositing a gallium-containing thin film of the present invention.
본 발명의 일 측면은 휘발성 및 안정성이 우수하여 갈륨 함유 박막의 전구체로 매우 유용한 갈륨 화합물을 제공하는 것으로, 본 발명의 갈륨 화합물은 하기 화학식 1로 표시된다.One aspect of the present invention is to provide a gallium compound that is very useful as a precursor for gallium-containing thin films due to its excellent volatility and stability. The gallium compound of the present invention is represented by the following formula (1).
[화학식 1][Formula 1]
상기 화학식 1에서,In Formula 1,
R1 및 R2는 서로 독립적으로 C1-C10알킬 또는 
이고;R 1 and R 2 are independently C1-C10 alkyl or ego;
R3 및 R'는 서로 독립적으로 C1-C10알킬 또는 C2-C10알케닐이다.R 3 and R' are independently C1-C10 alkyl or C2-C10 alkenyl.
본 발명의 다른 측면은 상기 갈륨 화합물의 제조방법을 제공하는 것으로, 본 발명의 갈륨 화합물의 제조방법은 하기 화학식 4의 알릴아민 화합물을 리튬화시킨 후 하기 화학식 5의 디알킬갈륨 할라이드 화합물와 반응시켜 하기 화학식 1-1의 갈륨 화합물을 제조하는 단계;를 포함한다.Another aspect of the present invention is to provide a method for producing the gallium compound. The method for producing the gallium compound of the present invention is to lithium an allylamine compound of the following formula (4) and then reacting with a dialkyl gallium halide compound of the formula (5). It includes preparing a gallium compound of Formula 1-1.
[화학식 1-1][Formula 1-1]
[화학식 4][Formula 4]
[화학식 5][Formula 5]
상기 화학식 1-1, 4 및 5에서,In Formulas 1-1, 4 and 5,
R2a는 C1-C10알킬이고;R 2a is C1-C10 alkyl;
R1a는 C1-C10알킬이고;R 1a is C1-C10 alkyl;
R3 및 R'는 서로 독립적으로 C1-C10알킬 또는 C2-C10알케닐이고;R 3 and R' are independently C1-C10 alkyl or C2-C10 alkenyl;
hal은 할로겐이다.hal is halogen.
본 발명의 다른 측면은 상기 갈륨 화합물의 제조방법을 제공하는 것으로, 본 발명의 갈륨 화합물의 제조방법은 하기 화학식 4의 알릴아민 화합물을 리튬화시킨 후 하기 화학식 6의 알킬갈륨 디할라이드 화합물와 반응시켜 하기 화학식 1-2의 갈륨 화합물을 제조하는 단계;를 포함한다.Another aspect of the present invention is to provide a method for producing the gallium compound. The method for producing the gallium compound of the present invention is to lithium an allylamine compound of the following formula (4) and then reacting with an alkyl gallium dihalide compound of the formula (6) to produce It includes preparing a gallium compound of Formula 1-2.
[화학식 1-2][Formula 1-2]
[화학식 4][Formula 4]
[화학식 6][Formula 6]
상기 화학식 1-2, 4 및 6에서,In Formulas 1-2, 4 and 6,
R2a는 C1-C10알킬이고;R 2a is C1-C10 alkyl;
R3 및 R'는 서로 독립적으로 C1-C10알킬 또는 C2-C10알케닐이고;R 3 and R' are independently C1-C10 alkyl or C2-C10 alkenyl;
hal은 할로겐이다.hal is halogen.
본 발명의 또 다른 측면은 일 실시예에 따른 화학식 1로 표시되는 갈륨 화합물을 포함하는 갈륨 함유 박막증착용 조성물 및 이를 이용하여 갈륨 함유 박막의 형성방법을 제공한다.Another aspect of the present invention provides a composition for depositing a gallium-containing thin film containing a gallium compound represented by Formula 1 according to an embodiment, and a method of forming a gallium-containing thin film using the same.
본 발명의 또 다른 측면은 일 실시예에 따른 화학식 1로 표시되는 갈륨 화합물을 이용하여 갈륨 함유 박막의 형성방법을 제공한다.Another aspect of the present invention provides a method of forming a gallium-containing thin film using a gallium compound represented by Formula 1 according to an embodiment.
본 발명의 갈륨 화합물은 열적 안정성이 양호하며 휘발성이 높고 응집력이 우수하여 갈륨 함유 박막의 전구체로 유용하고 나아가 기판과의 흡착이 우수하여 보다 양질의 갈륨 함유 박막을 제조할 수 있다. 또한, 본 발명의 갈륨 화합물은 실온 및 취급이 가능한 압력 하에서 고체 또는 액체 상태로 존재하여 취급이 용이하다. 또한, 본 발명의 갈륨 화합물은 상온에서 고체 또는 액상으로 존재함에 따라 대면적 기판에 균일한 농도로 공급되어 박막 두께의 균일성이 우수하다 또한, 본 발명의 갈륨 화합물은 높은 공정온도 중에도 분해되지 않으며, 저장안정성이 우수하다.The gallium compound of the present invention has good thermal stability, high volatility, and excellent cohesiveness, so it is useful as a precursor for gallium-containing thin films. Furthermore, it has excellent adsorption with a substrate, making it possible to produce higher quality gallium-containing thin films. In addition, the gallium compound of the present invention exists in a solid or liquid state at room temperature and a manageable pressure, making it easy to handle. In addition, since the gallium compound of the present invention exists in a solid or liquid state at room temperature, it is supplied at a uniform concentration to a large-area substrate and has excellent thin film thickness uniformity. Additionally, the gallium compound of the present invention does not decompose even during high processing temperatures and does not decompose. , Excellent storage stability.
또한, 본 발명의 갈륨 화합물 또는 이를 포함하는 박막증착용 조성물을 이용하여 갈륨 함유 박막의 제조시, 높은 증착율로 우수한 응집력을 가져 고밀도 및 고순도의 균일한 박막을 제조할 수 있다. In addition, when manufacturing a gallium-containing thin film using the gallium compound of the present invention or a composition for thin film deposition containing the gallium compound, it is possible to produce a uniform thin film with high density and high purity due to excellent cohesion at a high deposition rate.
또한, 본 발명의 갈륨 함유 박막의 제조방법은 상기 갈륨 화합물 또는 이를 포함하는 갈륨 함유 박막증착용 조성물을 이용하여 갈륨 함유 박막을 제조함으로써 열적 안정성 및 내구성이 뛰어난 고품질의 갈륨 함유 박막의 제조가 가능하다. In addition, the method for manufacturing a gallium-containing thin film of the present invention enables the production of a high-quality gallium-containing thin film with excellent thermal stability and durability by manufacturing a gallium-containing thin film using the gallium compound or a composition for gallium-containing thin film deposition containing the gallium compound. .
도 1 - 실시예 1에서 제조된 갈륨 화합물 1의 TGA 분석 결과Figure 1 - TGA analysis results of gallium compound 1 prepared in Example 1
도 2 - 실시예 1에서 제조된 갈륨 화합물 1의 DSC 분석 결과Figure 2 - DSC analysis results of gallium compound 1 prepared in Example 1
도 3 - 갈륨 화합물 1의 주입 시간에 따른 갈륨 함유 박막의 주기당 성장률Figure 3 - Growth rate per cycle of gallium-containing thin films as a function of injection time of gallium compound 1.
이하, 본 발명에 대하여 보다 구체적으로 설명한다. 이 때 사용되는 기술 용어 및 과학 용어에 있어서 다른 정의가 없다면, 이 발명이 속하는 기술 분야에서 통상의 지식을 가진 자가 통상적으로 이해하고 있는 의미를 가지며, 하기의 설명에서 본 발명의 요지를 불필요하게 흐릴 수 있는 공지 기능 및 구성에 대한 설명은 생략한다.Hereinafter, the present invention will be described in more detail. Unless otherwise defined, the technical and scientific terms used herein have meanings commonly understood by those skilled in the art to which this invention pertains, and the following description will not unnecessarily obscure the gist of the present invention. Descriptions of possible notification functions and configurations are omitted.
본 명세서에서 사용되는 단수 형태는 문맥에서 특별한 지시가 없는 한 복수 형태도 포함하는 것으로 의도할 수 있다.As used herein, the singular forms “a,” “an,” and “the” are intended to include the plural forms as well, unless the context clearly dictates otherwise.
본 명세서에 기재된, "포함한다"는 "구비한다", "함유한다", "가진다" 또는 "특징으로 한다" 등의 표현과 등가의 의미를 가지는 개방형 기재이며, 추가로 열거되어 있지 않은 요소, 재료 또는 공정을 배제하지 않는다.As used herein, “comprises” is an open description that has the equivalent meaning to expressions such as “comprises,” “contains,” “has,” or “characterized by” elements that are not additionally listed; Does not exclude materials or processes.
본 명세서의 용어, "갈륨 화합물"은 화학식 1로 대표될 수 있으며, "갈륨 전구체" 또는 "갈륨 전구체 화합물" 등의 표현과 등가의 의미를 가진다.As used herein, the term “gallium compound” may be represented by Chemical Formula 1 and has an equivalent meaning to expressions such as “gallium precursor” or “gallium precursor compound.”
본 명세서의 용어, "열적 안정성"은 지속적인 가온 공정 또는 높은 온도의 공정 중에도 물성이 변화되지 않는 것을 의미하는 것일 수 있으며, 구체적으로 상술된 가혹조건 하에 장기적으로 노출되어도 구조 변화를 일으키지 않는 것을 의미한다.As used herein, the term “thermal stability” may mean that physical properties do not change even during a continuous heating process or a high temperature process, and specifically means that no structural change occurs even when exposed to the harsh conditions described above for a long period of time. .
본 명세서에 기재된 "알킬"은 탄소수 1 내지 10, 바람직하게 탄소수 1 내지 6, 보다 바람직하게 탄소수 1 내지 4를 가진 포화된 직쇄상 또는 분지상의 비-고리(cyclic) 탄화수소를 의미한다. "저급 알킬"은 탄소수가 1 내지 4인 직쇄상 또는 분지상 알킬을 의미한다. 대표적인 포화 직쇄상 알킬은 메틸, 에틸, n-프로필, n-부틸, n-펜틸, n-헥실, n-헵틸, n-옥틸, n-노닐과 n-데실을 포함하고, 반면에 포화 분지상 알킬은 이소프로필, sec-부틸, 이소부틸, tert-부틸, 이소펜틸, 2-메틸헥실, 3-메틸부틸, 2-메틸펜틸, 3-메틸펜틸, 4-메틸펜틸, 2-메틸헥실, 3-메틸헥실, 2-메틸펜틸, 3-메틸펜틸, 4-메틸펜틸, 2-메틸헥실, 3-메틸헥실, 4-메틸헥실, 5- 메틸헥실, 2,3-디메틸부틸, 2,3-디메틸펜틸, 2,4-디메틸펜틸, 2,3-디메틸헥실, 2,4-디메틸헥실, 2,5-디메틸헥실, 2,2-디메틸펜틸, 2,2-디메틸헥실, 3,3-디메틸펜틸, 3,3-디메틸헥실, 4,4-디메틸헥실, 2-에틸펜틸, 3-에틸펜틸, 2-데틸헥실, 3-에틸헥실, 4-에틸헥실, 2-메틸-2-에틸펜틸, 2-메틸-3-에틸펜틸, 2-메틸-4-에틸펜틸, 2-메틸-2-에틸헥실, 2-메틸-3-에틸헥실, 2-메틸-4-에틸헥실, 2,2-디에틸펜틸, 3,3-디에틸헥실, 2,2-디에틸헥실, 및 3,3-디에틸헥실을 포함한다.As used herein, “alkyl” refers to a saturated straight-chain or branched non-cyclic hydrocarbon having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, and more preferably 1 to 4 carbon atoms. “Lower alkyl” means straight-chain or branched alkyl having 1 to 4 carbon atoms. Representative saturated straight-chain alkyls include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl and n-decyl, while saturated branched alkyls include Alkyl is isopropyl, sec-butyl, isobutyl, tert-butyl, isopentyl, 2-methylhexyl, 3-methylbutyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2-methylhexyl, 3 -Methylhexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 2,3-dimethylbutyl, 2,3- Dimethylpentyl, 2,4-dimethylpentyl, 2,3-dimethylhexyl, 2,4-dimethylhexyl, 2,5-dimethylhexyl, 2,2-dimethylpentyl, 2,2-dimethylhexyl, 3,3-dimethyl Pentyl, 3,3-dimethylhexyl, 4,4-dimethylhexyl, 2-ethylpentyl, 3-ethylpentyl, 2-dethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 2-methyl-2-ethylpentyl, 2-methyl-3-ethylpentyl, 2-methyl-4-ethylpentyl, 2-methyl-2-ethylhexyl, 2-methyl-3-ethylhexyl, 2-methyl-4-ethylhexyl, 2,2-di Includes ethylpentyl, 3,3-diethylhexyl, 2,2-diethylhexyl, and 3,3-diethylhexyl.
본 명세서에서 "C1-C10"와 같이 기재된 경우, 이는 탄소수가 1 내지 10개임을 의미한다. 예를 들어, C1-C4알킬은 탄소 수가 1 내지 4인 알킬을 의미한다. 구체적인 일례로 메틸(methyl), 에틸(ethyl), 프로필(propyl), 이소프로필(iso-propyl), 부틸(butyl), 이소부틸(iso-butyl) 또는 tert-부틸(tert-butyl)일 수 있다.When written as “C1-C10” in this specification, it means that the number of carbon atoms is 1 to 10. For example, C1-C4alkyl refers to alkyl having 1 to 4 carbon atoms. Specific examples may be methyl, ethyl, propyl, iso-propyl, butyl, iso-butyl, or tert-butyl. .
본 명세서에 기재된 "알케닐"은 2 내지 10개, 바람직하게 2 내지 6의 탄소 원자, 보다 바람직하게 2 내지 4의 탄소원자 및 적어도 하나의 탄소-탄소 이중 결합을 포함하는 포화된 직쇄상 또는 분지상 비-고리 탄화수소를 의미한다. 대표적인 직쇄상 및 분지상 (C2-C10) 알케닐은 비닐, 알릴, 1-부테닐, 2-부테닐, 이소부테닐, 1-펜테닐, 2-펜테닐, 3-메틸-1-부테닐, 2-메틸-2-부테닐, 2,3-디메틸-2-부테닐, 1-헥세닐(hexenyl), 2-헥세닐, 3-헥세닐, 1-헵테닐, 2-헵테닐, 3-헵테닐, 1-옥테닐, 2-옥테닐, 3옥테닐, 1-노네닐(nonenyl), 2-노네닐, 3-노네닐, 1-데세닐, 2-데세닐, 및 3-데세닐을 포함한다. 이러한 알케닐 그룹은 선택적으로 치환될 수 있다.As used herein, “alkenyl” refers to a saturated straight-chain or branched group containing 2 to 10 carbon atoms, preferably 2 to 6 carbon atoms, more preferably 2 to 4 carbon atoms and at least one carbon-carbon double bond. refers to terrestrial non-cyclic hydrocarbons. Representative straight-chain and branched (C2-C10) alkenyls include vinyl, allyl, 1-butenyl, 2-butenyl, isobutenyl, 1-pentenyl, 2-pentenyl, 3-methyl-1-butenyl, 2-methyl-2-butenyl, 2,3-dimethyl-2-butenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 1-heptenyl, 2-heptenyl, 3- Heptenyl, 1-octenyl, 2-octenyl, 3-octenyl, 1-nonenyl, 2-nonenyl, 3-nonenyl, 1-decenyl, 2-decenyl, and 3-decenyl Includes. These alkenyl groups may be optionally substituted.
본 발명의 일 측면은 갈륨 함유 박막의 전구체로 매우 유용하게 사용가능한 갈륨 화합물을 제공하는 것으로, 본 발명의 갈륨 화합물은 하기 화학식 1로 표시된다.One aspect of the present invention is to provide a gallium compound that can be very useful as a precursor for a gallium-containing thin film. The gallium compound of the present invention is represented by the following formula (1).
[화학식 1][Formula 1]
상기 화학식 1에서,In Formula 1,
R1 및 R2는 서로 독립적으로 C1-C10알킬 또는 
이고;R 1 and R 2 are independently C1-C10 alkyl or ego;
R3 및 R'는 서로 독립적으로 C1-C10알킬 또는 C2-C10알케닐이다.R 3 and R' are independently C1-C10 alkyl or C2-C10 alkenyl.
일 실시예에 따른 상기 화학식 1에서 상기 R2는 C1-C10알킬, C1-C6알킬 또는 C1-C4알킬일 수 있다.In Formula 1 according to one embodiment, R 2 may be C1-C10 alkyl, C1-C6 alkyl, or C1-C4 alkyl.
일 실시예에 따른 상기 화학식 1에서 상기 R1, R2 및 R3는 서로 독립적으로 C1-C10알킬, C1-C6알킬 또는 C1-C4알킬일 수 있다.In Formula 1 according to one embodiment, R 1 , R 2 and R 3 may independently be C1-C10 alkyl, C1-C6 alkyl, or C1-C4 alkyl.
일 구체예에 있어서, 상기 R1, R2 및 R3는 서로 독립적으로 메틸 또는 에틸일 수 있다.In one embodiment, R 1 , R 2 and R 3 may each independently be methyl or ethyl.
일 실시예에 따른 상기 화학식 1에서 상기 R1 및 R2는 서로 독립적으로 C1-C10알킬이고, R3는 알릴일 수 있다.In Formula 1 according to one embodiment, R 1 and R 2 may each independently be C1-C10 alkyl, and R 3 may be allyl.
바람직하게 일 실시예에 있어서, 상기 갈륨 화합물은 하기 화학식 2로 표시될 수 있다.Preferably, in one embodiment, the gallium compound may be represented by the following formula (2).
[화학식 2][Formula 2]
상기 화학식 2에서,In Formula 2,
R1 및 R2는 서로 독립적으로 C1-C4알킬이다.R 1 and R 2 are independently C1-C4 alkyl.
일 구체예에 있어서, 상기 R1 및 R2는 서로 독립적으로 메틸, 에틸, 이소프로필 또는 t-부틸일 수 있다.In one embodiment, R 1 and R 2 may independently be methyl, ethyl, isopropyl, or t-butyl.
일 실시예에 따른 상기 화학식 1에서 상기 R1은 
이고, R'는 C1-C10알킬 또는 알릴이고, R2는 C1-C10알킬이고, R3는 C1-C10알킬 또는 알릴일 수 있다.In Formula 1 according to one embodiment, R 1 is , R' may be C1-C10 alkyl or allyl, R 2 may be C1-C10 alkyl, and R 3 may be C1-C10 alkyl or allyl.
바람직하게 일 실시예에 있어서, 상기 갈륨 화합물은 하기 화학식 3으로 표시될 수 있다.Preferably, in one embodiment, the gallium compound may be represented by the following formula (3).
[화학식 3][Formula 3]
상기 화학식 3에서,In Formula 3 above,
R2는 C1-C4알킬이고;R 2 is C1-C4alkyl;
R''는 C1-C4알킬 또는 알릴이다.R'' is C1-C4alkyl or allyl.
일 구체예에 있어서, 상기 R2는 메틸 또는 에틸일 수 있고, R''는 메틸, 에틸, 이소프로필 또는 알릴일 수 있다.In one embodiment, R 2 may be methyl or ethyl, and R'' may be methyl, ethyl, isopropyl, or allyl.
구체적으로 일 실시예에 따른 갈륨 화합물은 하기 화합물에서 선택될 수 있으나, 이에 한정이 있는 것은 아니다.Specifically, the gallium compound according to one embodiment may be selected from the following compounds, but is not limited thereto.
본 발명의 갈륨 화합물은 중심금속인 갈륨(Ga)에 알킬알릴아미노 리간드 또는 디알릴아미노 리간드가 결합된 구조로, 이러한 알릴아미노 리간드의 도입으로 인하여 열안정성 및 반응성이 현저하게 향상되는 동시에 휘발성이 높아 양질의 박막을 제조할 수 있다.The gallium compound of the present invention has a structure in which an alkylylamino ligand or diallylamino ligand is bonded to the central metal gallium (Ga). Due to the introduction of this allylamino ligand, thermal stability and reactivity are significantly improved and at the same time, it is highly volatile. High-quality thin films can be manufactured.
또한 본 발명의 갈륨 화합물은 상온 및 상압에서 고체 또는 액체 형태로 존재하므로, 저장안정성이 높고, 휘발성이 뛰어나 이를 갈륨 함유 박막증착용 전구체로 이용하여 밀도가 높은 고순도의 갈륨 함유 박막을 제조할 수 있다.In addition, since the gallium compound of the present invention exists in solid or liquid form at room temperature and pressure, it has high storage stability and excellent volatility, so it can be used as a precursor for deposition of gallium-containing thin films to produce high-density, high-purity gallium-containing thin films. .
원자층 증착(ALD)에 있어서, 반응물은 휘발성이 높고, 물질이 안정해야 하며, 반응성이 높아야 한다. 이에 대부분의 반도체 제조사(칩메이커)에서는 액상의 전구체의 공정상에 이점들로 인하여 액상의 전구체를 선호한다. 하지만 이러한 이점에도 불구하고 아직도 고체상의 전구체들이 사용되고 있는데, 이는 액상 전구체에 비하여 값이 싸고, 공정 중 불안전 분해, 또는 낮은 반응성 등으로 인한 박막의 오염도가 심하여 신뢰성이 떨어지는 단점들이 액상 전구체에 비하여 적기 때문이다.In atomic layer deposition (ALD), the reactants must be highly volatile, the material must be stable, and the reactivity must be high. Accordingly, most semiconductor manufacturers (chip makers) prefer liquid precursors due to their advantages in the process. However, despite these advantages, solid precursors are still used because they are cheaper than liquid precursors and have fewer disadvantages than liquid precursors, such as unreliability due to severe contamination of thin films due to unstable decomposition or low reactivity during the process. am.
본 발명의 다른 측면은 상기 갈륨 화합물의 제조방법을 제공하는 것이다.Another aspect of the present invention is to provide a method for producing the gallium compound.
일 실시예에 따른 갈륨 화합물의 제조방법은 하기 화학식 4의 알릴아민 화합물을 리튬화시킨 후 하기 화학식 5의 디알킬갈륨 할라이드 화합물와 반응시켜 하기 화학식 1-1의 갈륨 화합물을 제조하는 단계;를 포함한다.A method for producing a gallium compound according to an embodiment includes preparing a gallium compound of the formula 1-1 by lithiuming an allylamine compound of the formula 4 below and then reacting it with a dialkyl gallium halide compound of the formula 5 below. .
[화학식 1-1][Formula 1-1]
[화학식 4][Formula 4]
[화학식 5][Formula 5]
상기 화학식 1-1, 4 및 5에서,In Formulas 1-1, 4 and 5,
R2a는 C1-C10알킬이고;R 2a is C1-C10 alkyl;
R1a는 C1-C10알킬이고;R 1a is C1-C10 alkyl;
R3 및 R'는 서로 독립적으로 C1-C10알킬 또는 C2-C10알케닐이고;R 3 and R' are independently C1-C10 alkyl or C2-C10 alkenyl;
hal은 할로겐이다.hal is halogen.
일 실시예에 따른 갈륨 화합물의 제조방법은 하기 화학식 4의 알릴아민 화합물을 리튬화시킨 후 하기 화학식 6의 알킬갈륨 디할라이드 화합물와 반응시켜 하기 화학식 1-2의 갈륨 화합물을 제조하는 단계;를 포함한다.A method for producing a gallium compound according to an embodiment includes preparing a gallium compound of the formula 1-2 by lithiuming an allylamine compound of the formula 4 below and reacting it with an alkylgallium dihalide compound of the formula 6 below. .
[화학식 1-2][Formula 1-2]
[화학식 4][Formula 4]
[화학식 6][Formula 6]
상기 화학식 1-2, 4 및 6에서,In Formulas 1-2, 4 and 6,
R2a는 C1-C10알킬이고;R 2a is C1-C10 alkyl;
R3 및 R'는 서로 독립적으로 C1-C10알킬 또는 C2-C10알케닐이고;R 3 and R' are independently C1-C10 alkyl or C2-C10 alkenyl;
hal은 할로겐이다.hal is halogen.
일 실시예에 따른 갈륨 화합물의 제조방법은 일례로 상기와 같은 방법으로 제조될 수 있으나, 이외에 당업자가 인식할 수 있는 범위 내에서 가능한 방법이라면 모두 가능하다.The method for producing a gallium compound according to an embodiment may be, for example, produced by the same method as described above, but any other method is possible within the range recognized by a person skilled in the art.
일 실시예에 있어서, 상기 리튬화는 상기 화학식 4의 알릴아민 화합물을 탄소수 1 내지 10의 알킬리튬과 반응시키는 단계로, 통상 유기화합물의 리튬화에 사용될 수 있는 알킬리튬 화합물이 제한 없이 사용될 수 있다. 일례로 상기 탄소수 1 내지 10의 알킬리튬은 메틸리튬, 에틸리튬, 이소프로필리튬, n-부틸리튬, sec-부틸리튬, tert-부틸리튬, n-데실리튬 및 tert-옥틸리튬으로 이루어진 군으로부터 선택된 1종 이상일 수 있으나 이에 제한되는 것은 아니다. 이 중, 바람직하게는 n-부틸리튬, sec-부틸리튬, tert-부틸리튬 등이 사용될 수 있다.In one embodiment, the lithiation is a step of reacting the allylamine compound of Formula 4 with alkyl lithium having 1 to 10 carbon atoms, and alkyl lithium compounds that can be commonly used for lithiation of organic compounds can be used without limitation. . For example, the alkyl lithium having 1 to 10 carbon atoms is selected from the group consisting of methyl lithium, ethyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, n-decyl lithium and tert-octyl lithium. There may be more than one type, but it is not limited thereto. Among these, n-butyllithium, sec-butyllithium, tert-butyllithium, etc. can be preferably used.
구체적으로, 상기 화학식 4의 알릴아민 화합물을 10 ℃ 미만, 바람직하게는 10 내지 -10 ℃로 냉각하고, 용매를 투입한 다음, 탄소수 1 내지 10의 알킬리튬을 투입한 후, NMR 측정을 통해 상기 화학식 4의 알릴아민 화합물의 NH peak가 사라질 때까지 10 내지 30 ℃, 또는 20 내지 25 ℃에서 교반시켜 리튬화를 수행할 수 있다.Specifically, the allylamine compound of Formula 4 is cooled to less than 10°C, preferably to 10 to -10°C, a solvent is added, and then alkyllithium having 1 to 10 carbon atoms is added, and then the above-mentioned amine compound is measured through NMR measurement. Lithiumization can be performed by stirring at 10 to 30° C., or 20 to 25° C., until the NH peak of the allylamine compound of Formula 4 disappears.
상술된 리튬화 단계를 거친 반응중간체와 상기 화학식 5의 디알킬갈륨 할라이드 화합물 또는 상기 화학식 6의 알킬갈륨 디할라이드 화합물과의 금속화를 통해 목적하는 갈륨 화합물(화학식 1-1 또는 화학식 1-2)을 수득할 수 있다.The desired gallium compound (Formula 1-1 or Formula 1-2) is obtained by metallization with the reaction intermediate that has undergone the above-described lithiation step and the dialkyl gallium halide compound of Formula 5 or the alkyl gallium dihalide compound of Formula 6. can be obtained.
구체적으로, 리튬화 단계를 거친 반응중간체를 10 ℃ 미만, 바람직하게는 10 내지 -10 ℃로 냉각시킨 다음, 상기 화학식 5의 디알킬갈륨 할라이드 화합물 또는 상기 화학식 6의 알킬갈륨 디할라이드 화합물은 헥산 등의 유기용매 중에 분산되거나 용해시켜 냉각된 반응중간체에 천천히 주입한 다음, 5시간 이상, 또는 10시간 이상, 바람직하게는 15 내지 20시간동안 10 내지 30 ℃, 또는 20 내지 25 ℃에서 교반하여 금속화 반응을 수행할 수 있다.Specifically, the reaction intermediate that has undergone the lithiation step is cooled to less than 10° C., preferably 10 to -10° C., and then the dialkyl gallium halide compound of Formula 5 or the alkyl gallium dihalide compound of Formula 6 is added to hexane, etc. is dispersed or dissolved in an organic solvent and slowly injected into the cooled reaction intermediate, and then stirred at 10 to 30° C., or 20 to 25° C. for 5 hours or more, or 10 hours or more, preferably 15 to 20 hours, to metallize. The reaction can be carried out.
일 실시예에 있어서, 상기 반응은 질소, 아르곤 등의 비활성 기체 분위기 하에서 수행될 수 있다.In one embodiment, the reaction may be performed under an inert gas atmosphere such as nitrogen or argon.
본 발명의 또 다른 측면은 일 실시예에 따른 화학식 1로 표시되는 갈륨 화합물을 포함하는 갈륨 함유 박막증착용 조성물 및 이를 이용하여 갈륨 함유 박막의 형성방법을 제공한다.Another aspect of the present invention provides a composition for depositing a gallium-containing thin film containing a gallium compound represented by Formula 1 according to an embodiment, and a method of forming a gallium-containing thin film using the same.
일 실시예에 따른 박막증착용 조성물은 구체적으로 인듐 갈륨 아연 산화물(IGZO) 박막증착용일 수 있다.The composition for thin film deposition according to one embodiment may be specifically for indium gallium zinc oxide (IGZO) thin film deposition.
상술된 갈륨 화합물 이외에, 인듐 전구체 및 아연 전구체를 더 포함할 수 있다.In addition to the gallium compounds described above, it may further include an indium precursor and a zinc precursor.
상기 인듐 전구체는 C1-C6알킬인듐이고, 아연 전구체는 C1-C6알킬아연일 수 있으며, 구체적으로 상기 인듐 전구체는 트리메틸인듐(Trimethylindium; TMI) 또는 디메틸아미노프로필디메틸인듐(3-(Dimethylamino)propryl](dimethyl)indium; DADI)일 수 있으며, 상기 아연 전구체는 디에틸징크(diethylzinc; DEZ)일 수 있으나, 이에 한정되는 것은 아니다.The indium precursor may be C1-C6 alkyl indium, and the zinc precursor may be C1-C6 alkyl zinc. Specifically, the indium precursor may be trimethylindium (TMI) or dimethylaminopropyldimethylindium (3-(Dimethylamino)propryl). (dimethyl)indium; DADI), and the zinc precursor may be diethylzinc (DEZ), but is not limited thereto.
상기 인듐 전구체 : 갈륨 전구체: 아연 전구체의 몰비는 1 내지 10 : 1 내지 10 : 1 내지 10일 수 있으며, 구체적으로 1 내지 5 : 1 내지 5 : 1 내지 5, 보다 구체적으로 1 : 1 : 1일 수 있다.The molar ratio of the indium precursor: gallium precursor: zinc precursor may be 1 to 10:1 to 10:1 to 10, specifically 1 to 5:1 to 5:1 to 5, more specifically 1:1:1. You can.
본 발명의 또 다른 측면은 일 실시예에 따른 화학식 1로 표시되는 갈륨 화합물을 이용하여 갈륨 함유 박막의 형성방법을 제공한다.Another aspect of the present invention provides a method of forming a gallium-containing thin film using a gallium compound represented by Formula 1 according to an embodiment.
상기 갈륨 함유 박막의 제조방법은 당업계에서 사용되는 통상적인 방법, 구체적으로는 원자층 증착법(ALD), 화학기상 증착법(CVD), 유기금속 화학기상 증착법(MOCVD), 저압 화학기상 증착법(LPCVD), 플라즈마강화 화학기상 증착법(PECVD) 또는 플라즈마강화 원자층 증착법(PEALD)일 수 있다.The method of manufacturing the gallium-containing thin film is a common method used in the industry, specifically atomic layer deposition (ALD), chemical vapor deposition (CVD), metal organic chemical vapor deposition (MOCVD), and low pressure chemical vapor deposition (LPCVD). , it may be plasma-enhanced chemical vapor deposition (PECVD) or plasma-enhanced atomic layer deposition (PEALD).
보다 바람직하게 일 실시예에 따른 상기 인듐 함유 박막의 제조방법은 원자층 증착법(ALD), 화학기상 증착법(CVD), 유기금속 화학기상 증착법(MOCVD) 등 일 수 있다.More preferably, the method for manufacturing the indium-containing thin film according to an embodiment may be atomic layer deposition (ALD), chemical vapor deposition (CVD), or metal organic chemical vapor deposition (MOCVD).
일 실시예에 따른 갈륨 함유 박막은 당업계에서 사용되는 통상적인 방법으로 제조될 수 있으며, 일례로 유기금속 화학기상 증착법(MOCVD), 원자층 증착법(ALD), 저압 기상 증착법(LPCVD), 플라즈마 강화 기상 증착법 (PECVD) 또는 플라즈마 강화 원자층 증착법(PEALD)등을 들 수 있으나, 바람직하게 원자층 증착법(ALD) 또는 플라즈마 강화 원자층 증착법(PEALD)일 수 있다.A gallium-containing thin film according to an embodiment may be manufactured by a common method used in the art, for example, metal organic chemical vapor deposition (MOCVD), atomic layer deposition (ALD), low pressure vapor deposition (LPCVD), and plasma enhanced Examples include vapor deposition (PECVD) or plasma enhanced atomic layer deposition (PEALD), but atomic layer deposition (ALD) or plasma enhanced atomic layer deposition (PEALD) is preferred.
일 실시예에 있어서, 본 발명의 갈륨 함유 박막은 원자층 증착법(ALD)에 의해 제조될 수 있다.In one embodiment, the gallium-containing thin film of the present invention may be manufactured by atomic layer deposition (ALD).
일 실시예에 따른 갈륨 함유 박막의 제조방법은 상기 갈륨 화합물을 기판 상에 증착하여 박막을 형성하는 단계를 포함하며, 구체적으로는 a) 기판 상에 상기 갈륨 화합물을 흡착시키는 단계; b) 미흡착된 갈륨 화합물을 퍼지하는 단계; c) 반응가스를 주입하여 갈륨 함유 박막을 형성시키는 단계; 및 d) 잔류 반응가스 및 반응 부산물을 퍼지하는 단계;를 포함할 수 있다.A method of manufacturing a gallium-containing thin film according to an embodiment includes forming a thin film by depositing the gallium compound on a substrate, and specifically, a) adsorbing the gallium compound on the substrate; b) purging non-adsorbed gallium compounds; c) forming a gallium-containing thin film by injecting a reaction gas; and d) purging residual reaction gas and reaction by-products.
일 실시예에 따른 갈륨 함유 박막의 제조방법은 상기 갈륨 화합물과 인듐 전구체 및 아연 전구체 중에서 선택된 1종 이상을 기재 상에 증착하여 단층 또는 다층 박막을 형성하는 단계를 포함할 수 있으며, 상기 갈륨 화합물, 인듐 전구체 및 아연 전구체를 기판 상에 동시에 증착하거나, 상기 갈륨 화합물, 인듐 전구체 및 아연 전구체를 혼합한 후 기판 상에 증착하여 단층 구조의 박막을 형성할 수 있고, 인듐 전구체, 상기 갈륨 화합물 및 아연 전구체를 기재 상에 순차적으로 증착하여 다층 구조의 박막을 형성할 수도 있다. 구체적으로 상기 인듐 전구체는 트리메틸인듐(Trimethylindium; TMI)일 수 있으며, 상기 아연 전구체는 디에틸징크(diethylzinc; DEZ)일 수 있으나, 이에 한정되는 것은 아니다. 상기 다층 구조의 박막은 인듐-갈륨-아연 산화막(IGZO 박막)일 수 있으며, 인듐 : 갈륨 : 아연의 조성비는 1 내지 10 : 1 내지 10 : 1 내지 10일 수 있으며, 구체적으로 1 내지 5 : 1 내지 5 : 1 내지 5, 보다 구체적으로 1 : 1 : 1일 수 있다.A method of manufacturing a gallium-containing thin film according to an embodiment may include forming a single-layer or multi-layer thin film by depositing the gallium compound and at least one selected from an indium precursor and a zinc precursor on a substrate, wherein the gallium compound, The indium precursor and the zinc precursor can be deposited on the substrate simultaneously, or the gallium compound, the indium precursor, and the zinc precursor can be mixed and deposited on the substrate to form a thin film with a single-layer structure, and the indium precursor, the gallium compound, and the zinc precursor can be deposited on the substrate. may be sequentially deposited on a substrate to form a thin film with a multilayer structure. Specifically, the indium precursor may be trimethylindium (TMI), and the zinc precursor may be diethylzinc (DEZ), but are not limited thereto. The multilayer thin film may be an indium-gallium-zinc oxide film (IGZO thin film), and the composition ratio of indium:gallium:zinc may be 1 to 10:1 to 10:1 to 10, specifically 1 to 5:1. to 5:1 to 5, more specifically 1:1:1.
일 실시예에 따른 갈륨 함유 박막은 상기 갈륨 화합물을 이용하여 제조되며, 한정이 있는 것은 아니나 바람직하게 갈륨질화막, 갈륨산화막 또는 인듐-갈륨-아연 산화막일 수 있으며, 바람직하게 갈륨산화막 또는 인듐-갈륨-아연 산화막일 수 있다.The gallium-containing thin film according to one embodiment is manufactured using the gallium compound, and is not limited, but is preferably a gallium nitride film, a gallium oxide film, or an indium-gallium-zinc oxide film, and is preferably a gallium oxide film or an indium-gallium-zinc oxide film. It may be a zinc oxide film.
본 발명의 갈륨 함유 박막의 제조방법은 높은 휘발성 및 열안정성을 가지는 본 발명의 갈륨 화합물을 전구체로 사용하여 제조됨으로써 제조된 갈륨 함유 박막은 물리적, 전기적, 화학적 특성이 극히 우수하다.The method for producing a gallium-containing thin film of the present invention uses the gallium compound of the present invention, which has high volatility and thermal stability, as a precursor, and the produced gallium-containing thin film has extremely excellent physical, electrical, and chemical properties.
일 실시예에 따른 갈륨 함유 박막의 제조방법에서 본 발명의 갈륨 화합물의 주입온도는 상온(25℃내지 120℃일 수 있으며, 본 발명의 갈륨 화합물의 높은 휘발성으로 인해 갈륨 화합물이 증착될 기판의 온도는 100 내지 450℃이고, 챔버 내부 압력은 0.1 내지 10 torr일 수 있다.In the method for manufacturing a gallium-containing thin film according to an embodiment, the injection temperature of the gallium compound of the present invention may be room temperature (25°C to 120°C, and due to the high volatility of the gallium compound of the present invention, the temperature of the substrate on which the gallium compound will be deposited is 100 to 450°C, and the pressure inside the chamber may be 0.1 to 10 torr.
일 실시예에 따른 갈륨 함유 박막의 제조방법에서 사용되는 반응가스는 한정이 있는 것은 아니나, 수소(H2), 히드라진(N2H4), 디메틸히드라진(Me2N2H2), 오존(O3), 산소(O2), 물(H2O), 암모니아(NH3), 질소(N2), 실란(SiH4), 보란(BH3), 디보란(B2H6) 및 포스핀(PH3)에서 선택되는 하나 또는 하나이상의 혼합기체를 사용할 수 있으며, 상기 반응가스는 한정이 있는 것은 아니나, 10 내지 10,000 sccm의 유량으로 공급될 수 있으며, 구체적으로 50 내지 1,000 sccm으로 공급될 수 있다.The reaction gas used in the method for manufacturing a gallium-containing thin film according to an embodiment is not limited, but includes hydrogen (H 2 ), hydrazine (N 2 H 4 ), dimethylhydrazine (Me 2 N 2 H 2 ), and ozone ( O 3 ), oxygen (O 2 ), water (H 2 O), ammonia (NH 3 ), nitrogen (N 2 ), silane (SiH 4 ), borane (BH 3 ), diborane (B 2 H 6 ), and One or more mixed gases selected from phosphine (PH 3 ) can be used, and the reaction gas is not limited, but can be supplied at a flow rate of 10 to 10,000 sccm, specifically 50 to 1,000 sccm. It can be.
구체적으로 수증기(H2O), 산소(O2) 또는 오존(O3) 등의 산화성 반응가스 존재 하에서 증착이 이루어지는 경우 갈륨산화막이 형성될 수 있으며, 암모니아(NH3) 또는 하이드라진(N2H4) 등의 질소-함유 반응가스 존재 하에서 증착이 이루어 지는 경우에는 갈륨질화막이 형성될 수 있다.Specifically, when deposition is performed in the presence of oxidizing reaction gases such as water vapor (H 2 O), oxygen (O 2 ), or ozone (O 3 ), a gallium oxide film may be formed, and ammonia (NH 3 ) or hydrazine (N 2 H 4 ) If deposition is performed in the presence of a nitrogen-containing reaction gas such as, a gallium nitride film may be formed.
상기 퍼지 가스는 불활성 가스로, 한정이 있는 것은 아니나, 아르곤(Ar) 및 헬륨(He)에서 선택되는 하나 또는 둘 이상의 혼합기체일 수 있다.The purge gas is an inert gas, but is not limited thereto, and may be one or a mixture of two or more gases selected from argon (Ar) and helium (He).
일 실시예에 따른 갈륨 함유 박막의 제조방법에서 사용되는 기판은 Si, SiO2, Pt, TiN, Ge, SiGe, GaP, GaAs, SiC, SiGeC, InAs 및 InP 중 하나 이상의 반도체 재료를 포함하는 기판; SOI(Silicon On Insulator) 기판; 석영 기판; 또는 디스플레이용 유리 기판; 폴리이미드(polyimide), 폴리에틸렌 테레프탈레이트(PET, PolyEthylene Terephthalate), 폴리에틸렌 나프탈레이트(PEN, PolyEthylene Naphthalate), 폴리 메틸메타크릴레이트(PMMA, Poly Methyl MethAcrylate), 폴리카보네이트(PC, PolyCarbonate), 폴리에테르술폰(PES), 폴리에스테르(Polyester) 등의 가요성 플라스틱 기판; 등일 수 있으나, 이에 한정되는 것은 아니다.The substrate used in the method of manufacturing a gallium-containing thin film according to an embodiment includes a substrate containing one or more semiconductor materials selected from the group consisting of Si, SiO2, Pt, TiN, Ge, SiGe, GaP, GaAs, SiC, SiGeC, InAs, and InP; SOI (Silicon On Insulator) substrate; Quartz substrate; or a glass substrate for display; Polyimide, PolyEthylene Terephthalate (PET), PolyEthylene Naphthalate (PEN), Poly Methyl MethAcrylate (PMMA), Polycarbonate (PC, PolyCarbonate), Polyether Sulfone Flexible plastic substrates such as (PES) and polyester; It may be, but is not limited to this.
일 실시예에 따른 갈륨 함유 박막의 제조방법은 높은 휘발성과 높은 열적 안정성을 가지며, 이를 박막증착용 전구체로 사용함으로써 물리적, 전기적 및 화학적 특성이 매우 우수하며 고밀도 및 고순도의 양질의 균일한 갈륨 함유 박막을 형성할 수 있다.The method for manufacturing a gallium-containing thin film according to an embodiment has high volatility and high thermal stability, and by using it as a precursor for thin film deposition, the gallium-containing thin film has excellent physical, electrical and chemical properties, and has high density and high purity, and is of good quality and uniformity. can be formed.
이하, 실시예를 통하여 본 발명의 구성을 보다 구체적으로 설명하지만, 하기의 실시예들은 본 발명에 대한 이해를 돕기 위한 것으로서, 본 발명의 범위가 여기에 국한된 것은 아니다.Hereinafter, the configuration of the present invention will be described in more detail through examples. However, the following examples are intended to aid understanding of the present invention, and the scope of the present invention is not limited thereto.
이하 본 발명에 따른 갈륨 화합물의 합성은 별도로 언급되는 경우를 제외하고 비활성 아르곤 또는 질소 분위기 하에서 표준 슐렝크 플라스크 (Schlenk flask) 또는 퍼지박스(purge box)를 사용하여 수행하였다. 1H NMR 스펙트럼 및 원소 분석을 통해 수득된 갈륨 화합물의 구조를 분석하였다. 또한, 증착된 갈륨 함유 박막은 엘립소미터(Ellipsometer, Thermowave, Optiprobe 2600)를 이용하여 두께를 측정하였고, X-선 광전자 분석(XPS, X-ray Photoelectron Spectroscopy, ThermoFisher Scientific, K-Alpha+)을 이용하여 박막의 조성을 분석하였다.Hereinafter, the synthesis of the gallium compound according to the present invention was performed using a standard Schlenk flask or purge box under an inert argon or nitrogen atmosphere, except where otherwise noted. The structure of the obtained gallium compound was analyzed through 1 H NMR spectrum and elemental analysis. In addition, the thickness of the deposited gallium-containing thin film was measured using an ellipsometer (Ellipsometer, Thermowave, Optiprobe 2600) and X-ray photoelectron spectroscopy (XPS, X-ray Photoelectron Spectroscopy, ThermoFisher Scientific, K-Alpha+). The composition of the thin film was analyzed.
[실시예 1] 갈륨 화합물 1의 합성[Example 1] Synthesis of gallium compound 1
오븐에서 건조된 250ml 슐렝크 플라스크와 100ml 슐렝크 플라스크 2개를 퍼지박스에 넣고 30분 이상 퍼지를 진행하여 초자 내부의 수분을 최대한 제거하였다. A 250ml Schlenk flask and two 100ml Schlenk flasks dried in an oven were placed in a purge box and purged for more than 30 minutes to remove as much moisture inside the glassware as possible.
퍼지박스 내에서 250ml 슐렝크 플라스크에 diallyl amine 9.12ml (0.0739mol)을 가하고(A), 100ml 슐렝크 플라스크에 n-Butyl Lithium 2.5M in hexane 29.5ml (0.0739mol)을 가하였다(B). 이후 각 플라스크를 후드로 이동시켰다. acetone/dry ice bath를 이용하여 플라스크 A를 0°C로 냉각시키고, 질소를 불어주면서 hexane 100ml를 가하였다. 10℃ 이내로 유지된 플라스크 A에 플라스크 B의 용액을 가압이송 하였다. 이때 온도계를 확인하면서 천천히 넣어주고, 온도는 10℃이하를 유지하였다. 가압이송 완료 후 hexane 10ml를 플라스크 B에 넣고 워싱하여 플라스크 A로 추가 가압이송을 2회 진행하였다. NMR 측정을 통해 diallyl amine의 NH peak가 사라질 때까지 상온에서 반응을 진행하였다. 합성된 중간체(플라스크 A 내 존재)는 Benzen-d6 용매로 하여 1H NMR을 측정하였고, 측정 결과는 다음과 같다. 3.5624ppm (s, 2H), 5.0422ppm (d, 1H), 5.2178ppm (d, 1H), 6.0614ppm (s, 1H)In the purge box, 9.12ml (0.0739mol) of diallyl amine was added to a 250ml Schlenk flask (A), and 29.5ml (0.0739mol) of n-Butyl Lithium 2.5M in hexane was added to a 100ml Schlenk flask (B). Each flask was then moved to the hood. Flask A was cooled to 0°C using an acetone/dry ice bath, and 100ml of hexane was added while blowing nitrogen. The solution from flask B was pressurized and transferred to flask A, which was maintained within 10°C. At this time, it was added slowly while checking the thermometer, and the temperature was maintained below 10°C. After completion of pressurized transfer, 10 ml of hexane was added to flask B, washed, and further pressurized transferred to flask A twice. The reaction was carried out at room temperature until the NH peak of diallyl amine disappeared through NMR measurement. 1 H NMR was measured for the synthesized intermediate (present in flask A) using Benzen-d 6 solvent, and the measurement results are as follows. 3.5624ppm (s, 2H), 5.0422ppm (d, 1H), 5.2178ppm (d, 1H), 6.0614ppm (s, 1H)
이어서, 퍼지박스 내에서 100ml 슐렝크 플라스크에 dimethylgallium chloride 10g (0.0739mol)을 가하고(C), 이를 후드로 이동시킨 다음, hexane 30ml를 가하고 용해시켰다. acetone/dry ice bath를 이용하여 중간체가 들어있는 플라스크 A의 온도를 다시 0°C로 냉각시킨 후 동온도에서 플라스크 C의 용액을 플라스크 A로 가압이송 하였다. 이때 온도계를 확인하면서 천천히 넣어주었다. 이후 상온에서 18시간동안 반응을 진행하였다. 반응이 완료되면 여과하여 염을 제거하고, 진공건조를 통해 잔여 용매를 제거하여 흰색 고체의 갈륨 화합물 1을 11g(76%) 수득하였다(수율 76%).Next, 10 g (0.0739 mol) of dimethylgallium chloride was added to a 100 ml Schlenk flask in the purge box (C), moved to a hood, and then 30 ml of hexane was added and dissolved. The temperature of flask A containing the intermediate was cooled back to 0°C using an acetone/dry ice bath, and then the solution from flask C was pressurized and transferred to flask A at the same temperature. At this time, I added it slowly while checking the thermometer. Afterwards, the reaction proceeded at room temperature for 18 hours. When the reaction was completed, the salt was removed by filtration, and the remaining solvent was removed through vacuum drying to obtain 11 g (76%) of gallium compound 1 as a white solid (yield 76%).
1H NMR 400MHz(C6D6) : δ -0.1455 (s, 6H), 3.3457 (d, 4H), 4.9705 (d, 2H), 5.0128 (d, 2H), 5.5967 (m, 2H) 1 H NMR 400MHz(C 6 D 6 ): δ -0.1455 (s, 6H), 3.3457 (d, 4H), 4.9705 (d, 2H), 5.0128 (d, 2H), 5.5967 (m, 2H)
[실시예 2] 갈륨 화합물 2의 합성[Example 2] Synthesis of gallium compound 2
실시예 1의 diallyl amine 9.12ml (0.0739mol) 대신에 N-allylmethylamine 2.6g (0.0370 mol)을 사용하고, n-Butyl Lithium 2.5M in hexane 29.5ml (0.0739mol) 대신에 n-Butyl Lithium in hexane 2.5M 14.7ml (0.0370 mol)을 사용하고, dimethylgallium chloride 10g (0.0739mol) 대신에 dimethylgallium chloride 5g (0.0370 mol)을 사용한 것을 제외하고는 상기 실시예 1과 동일하게 반응시켜 갈륨 화합물 2를 투명한 액체로 8.54g(68%) 수득하였다(수율 68%).Instead of diallyl amine 9.12ml (0.0739mol) in Example 1, N-allylmethylamine 2.6g (0.0370 mol) was used, and instead of n-Butyl Lithium 2.5M in hexane 29.5ml (0.0739mol), n-Butyl Lithium in hexane 2.5 The reaction was carried out in the same manner as in Example 1, except that 14.7 ml (0.0370 mol) of M was used and 5 g (0.0370 mol) of dimethylgallium chloride was used instead of 10 g (0.0739 mol) of dimethylgallium chloride, and gallium compound 2 was converted into a transparent liquid. g (68%) was obtained (yield 68%).
1H NMR 400MHz(C6D6) : δ -0.1683 (t, 6H), 2.1513 (ss, 3H), 3.1657 (dd, 2H), 4.9576 (dd, 2H), 5.5988 (m, 1H) 1 H NMR 400MHz(C 6 D 6 ): δ -0.1683 (t, 6H), 2.1513 (ss, 3H), 3.1657 (dd, 2H), 4.9576 (dd, 2H), 5.5988 (m, 1H)
[실험예 1] 갈륨 화합물의 물질 분석[Experimental Example 1] Material analysis of gallium compounds
상기 실시예 1에서 제조된 갈륨 화합물 1의 열적 안정성 및 분해 온도를 측정하기 위해, 열무게 분석법(TGA) 및 시차주사열량법(DSC)을 이용하였다(측정조건: 질소 분위기 하에서 10Kmin-1로 500℃까지 승온). To measure the thermal stability and decomposition temperature of gallium compound 1 prepared in Example 1, thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) were used (measurement conditions: 500°C at 10Kmin -1 under a nitrogen atmosphere. (temperature increased to ℃).
TGA 및 DSC 분석 결과 그래프를 각각 도 1 및 도 2에 도시하였다.Graphs of the TGA and DSC analysis results are shown in Figures 1 and 2, respectively.
도 1로부터 실시예 1에서 제조된 갈륨화합물 1은 100℃ 부근에서 질량 감소가 일어나기 시작하여 219.7℃에서 약 50%의 질량 감소를 확인할 수 있다. 또한, 도 2로부터 약 225℃ 이하의 온도에서 열적으로 안정할 수 있는 것을 확인하였다. 이로부터 본 발명의 갈륨 화합물은 열안정성이 우수함을 알 수 있다.From Figure 1, it can be seen that the mass of gallium compound 1 prepared in Example 1 begins to decrease around 100°C, and the mass decreases by about 50% at 219.7°C. Additionally, it was confirmed from Figure 2 that it can be thermally stable at a temperature of about 225°C or lower. From this, it can be seen that the gallium compound of the present invention has excellent thermal stability.
[실시예 3 내지 7] 갈륨 함유 박막의 제조[Examples 3 to 7] Preparation of gallium-containing thin films
실시예 1에서 제조된 갈륨 화합물 1을 갈륨 함유 박막증착용 전구체로 사용하고, 반응가스로 오존(O3)을 사용하였으며, 오존의 농도는 220 g/㎥이었으며, 운반 가스 및 퍼지 가스로 아르곤(Ar)을 사용하여 원자층 증착법(Atomic layer deposition; ALD)에 의해 갈륨 함유 박막을 형성하였다. Gallium Compound 1 prepared in Example 1 was used as a precursor for deposition of gallium-containing thin films, ozone (O 3 ) was used as a reaction gas, the concentration of ozone was 220 g/㎥, and argon ( A gallium-containing thin film was formed by atomic layer deposition (ALD) using Ar).
실리콘 산화막을 기판으로 사용하였다. 증착 챔버 내부에 실리콘 산화막 기판을 로딩하고, 상기 기판 온도를 250℃로 설정하였다. 갈륨 화합물의 증기압을 적절히 유지하는 동시에 응축을 방지하기 위해 스테인리스 스틸 버블러(stainless steel bubbler) 내에 갈륨 화합물 1을 층진하고 30℃로 유지하였다. 반응 가스인 오존(O3)의 유속은 200 sccm으로 고정하고, 운반 가스(Ar)의 유속은 50 sccm으로 고정하고, 퍼지 가스(Ar)의 유속은 100 sccm으로 고정하였으며, 공정 압력을 1 Torr로 유지하였다. 갈륨 전구체를 이용한 박막 증착은 갈륨 전구체 주입 - 퍼지(Ar) - 오존(O3) 주입 - 퍼지(Ar)의 4개의 순차적 단계를 1주기로 하여 100주기를 반복하여 갈륨 함유 박막을 증착하였다. 하기 표 1에 상세한 증착 조건 및 결과를 나타내었다.A silicon oxide film was used as a substrate. A silicon oxide film substrate was loaded inside the deposition chamber, and the substrate temperature was set to 250°C. In order to properly maintain the vapor pressure of the gallium compound and prevent condensation, gallium compound 1 was placed in a stainless steel bubbler and maintained at 30°C. The flow rate of ozone (O 3 ), a reaction gas, was fixed at 200 sccm, the flow rate of carrier gas (Ar) was fixed at 50 sccm, the flow rate of purge gas (Ar) was fixed at 100 sccm, and the process pressure was 1 Torr. It was maintained as . Thin film deposition using a gallium precursor was performed by repeating 100 cycles of four sequential steps: gallium precursor injection - purge (Ar) - ozone (O 3 ) injection - purge (Ar) to deposit a gallium-containing thin film. Table 1 below shows detailed deposition conditions and results.
| 실시예Example | ||||||
| 33 | 44 | 55 | 66 | 77 | ||
| 공정 압력 (Torr)Process pressure (Torr) | 1One | 1One | 1One | 1One | 1One | |
| 실리콘 기판 온도 (℃)Silicon substrate temperature (℃) | 250250 | 250250 | 250250 | 250250 | 250250 | |
|
갈륨 전구체gallium precursor |
가열온도 (℃)Heating temperature (℃) | 2525 | 2525 | 2525 | 2525 | 2525 |
| 주입 시간 (초)Injection time (seconds) | 1One | 33 | 55 | 1010 | 2020 | |
|
퍼지 (Ar)Fudge (Ar) |
유량 (sccm)Flow rate (sccm) | 100100 | 100100 | 100100 | 100100 | 100100 |
| 시간 (초)time (seconds) | 2020 | 2020 | 2020 | 2020 | 2020 | |
| 오존(O3)Ozone (O 3 ) | 유량 (sccm)Flow rate (sccm) | 200200 | 200200 | 200200 | 200200 | 200200 |
| 시간 (초)time (seconds) | 2020 | 2020 | 2020 | 2020 | 2020 | |
|
퍼지 (Ar)Fudge (Ar) |
유량 (sccm)Flow rate (sccm) | 100100 | 100100 | 100100 | 100100 | 100100 |
| 시간 (초)time (seconds) | 2020 | 2020 | 2020 | 2020 | 2020 | |
| 증착 횟수Number of depositions | 주기to give | 100100 | 100100 | 100100 | 100100 | 100100 |
| 박막 두께 (Å)Thin film thickness (Å) | 9797 | 108108 | 104104 | 111111 | 108108 | |
| GPC (Å)GPC (Å) | 0.970.97 | 1.081.08 | 1.041.04 | 1.111.11 | 1.081.08 | |
갈륨 화합물 1의 주입시간에 따른 주기당 성장률(growth per cycle; GPC)을 측정하여 이를 도 3에 도시하였다. 상기 표 1 및 도 3으로부터 본 발명에 따른 갈륨 전구체는 주입 시간 1 내지 3초까지는 GPC가 증가하고, 주입시간 3초부터는 GPC가 일정 수준으로 유지되어 갈륨 전구체의 주입 시간 3초부터 포화(Saturation)되어 갈륨 함유 박막의 성장률이 일정한 것을 확인할 수 있었다.The growth rate per cycle (GPC) according to the injection time of gallium compound 1 was measured and shown in FIG. 3. From Table 1 and Figure 3, the GPC of the gallium precursor according to the present invention increases from 1 to 3 seconds of injection time, and the GPC is maintained at a constant level from 3 seconds of injection time, resulting in saturation from 3 seconds of injection time of the gallium precursor. It was confirmed that the growth rate of the gallium-containing thin film was constant.
본 발명에 따른 갈륨 화합물은 우수한 열안정성 및 휘발성을 가져 갈륨 함유 박막의 전구체로 유용하며, 높은 증기압을 가지고 있어 박막 제조시 균일한 전구체 공급을 통하여 균일한 조성제어로 균일한 박막 증착이 가능하고, 고밀도 및 고순도의 갈륨 함유 박막을 용이하게 제조할 수 있다.The gallium compound according to the present invention has excellent thermal stability and volatility and is useful as a precursor for gallium-containing thin films. It has a high vapor pressure, enabling uniform thin film deposition through uniform composition control through uniform precursor supply during thin film production. High-density and high-purity gallium-containing thin films can be easily manufactured.
전술한 본 발명의 설명은 예시를 위한 것이며, 본 발명이 속하는 기술분야의 통상의 지식을 가진 자는 본 발명의 기술적 사상이나 필수적인 특징을 변경하지 않고서 다른 구체적인 형태로 쉽게 변형이 가능하다는 것을 이해할 수 있을 것이다. 그러므로 이상에서 기술한 실시예들은 모든 면에서 예시적인 것이며 한정적이 아닌 것으로 이해해야만 한다.The description of the present invention described above is for illustrative purposes, and those skilled in the art will understand that the present invention can be easily modified into other specific forms without changing the technical idea or essential features of the present invention. will be. Therefore, the embodiments described above should be understood in all respects as illustrative and not restrictive.
Claims (13)
- 하기 화학식 1로 표시되는 갈륨 화합물:A gallium compound represented by the following formula (1):[화학식 1][Formula 1]
상기 화학식 1에서,In Formula 1,R1 및 R2는 서로 독립적으로 C1-C10알킬 또는이고;R 1 and R 2 are independently C1-C10 alkyl or
ego;R3 및 R'는 서로 독립적으로 C1-C10알킬 또는 C2-C10알케닐이다.R 3 and R' are independently C1-C10 alkyl or C2-C10 alkenyl. - 제 1항에 있어서,According to clause 1,R2는 C1-C10알킬인, 갈륨 화합물.R 2 is C1-C10 alkyl, a gallium compound.
- 제 2항에 있어서,According to clause 2,R1, R2 및 R3는 서로 독립적으로 C1-C4알킬인, 갈륨 화합물.A gallium compound wherein R 1 , R 2 and R 3 are independently C1-C4alkyl.
- 제 2항에 있어서,According to clause 2,상기 갈륨 화합물은 하기 화학식 2 또는 3으로 표시되는 것인, 갈륨 화합물:The gallium compound is represented by the following formula 2 or 3:[화학식 2] [Formula 2]
[화학식 3][Formula 3]
상기 화학식 2 및 3에서,In Formulas 2 and 3,R1 및 R2는 서로 독립적으로 C1-C4알킬이고;R 1 and R 2 are independently C1-C4 alkyl;R''는 C1-C4알킬 또는 알릴이다.R'' is C1-C4alkyl or allyl. - 제 1항에 있어서,According to clause 1,상기 갈륨 화합물은 하기 화합물에서 선택되는 것인, 갈륨 화합물:The gallium compound is selected from the following compounds:
- 하기 화학식 4의 알릴아민 화합물을 리튬화시킨 후 하기 화학식 5의 디알킬갈륨 할라이드 화합물와 반응시켜 하기 화학식 1-1의 갈륨 화합물을 제조하는 단계;를 포함하는 갈륨 화합물의 제조방법.A method for producing a gallium compound comprising the step of preparing a gallium compound of Formula 1-1 by reacting an allylamine compound of Formula 4 below with a dialkyl gallium halide compound of Formula 5 after lithiuming an allylamine compound of Formula 4 below.[화학식 1-1][Formula 1-1]
[화학식 4][Formula 4]
[화학식 5][Formula 5]
상기 화학식 1-1, 4 및 5에서,In Formulas 1-1, 4 and 5,R2a는 C1-C10알킬이고;R 2a is C1-C10 alkyl;R1a는 C1-C10알킬이고;R 1a is C1-C10 alkyl;R3 및 R'는 서로 독립적으로 C1-C10알킬 또는 C2-C10알케닐이고;R 3 and R' are independently C1-C10 alkyl or C2-C10 alkenyl;hal은 할로겐이다.hal is halogen. - 하기 화학식 4의 알릴아민 화합물을 리튬화시킨 후 하기 화학식 6의 알킬갈륨 디할라이드 화합물와 반응시켜 하기 화학식 1-2의 갈륨 화합물을 제조하는 단계;를 포함하는 갈륨 화합물의 제조방법.A method for producing a gallium compound comprising the step of preparing a gallium compound of Formula 1-2 by reacting an allylamine compound of Formula 4 below with an alkyl gallium dihalide compound of Formula 6 after lithium.[화학식 1-2][Formula 1-2]
[화학식 4][Formula 4]
[화학식 6][Formula 6]
상기 화학식 1-2, 4 및 6에서,In Formulas 1-2, 4 and 6,R2a는 C1-C10알킬이고;R 2a is C1-C10 alkyl;R3 및 R'는 서로 독립적으로 C1-C10알킬 또는 C2-C10알케닐이고;R 3 and R' are independently C1-C10 alkyl or C2-C10 alkenyl;hal은 할로겐이다.hal is halogen. - 제 1항 내지 제 5항에서 선택되는 어느 한 항에 따른 갈륨 화합물을 포함하는 갈륨 함유 박막증착용 조성물. A composition for depositing a gallium-containing thin film, comprising the gallium compound according to any one of claims 1 to 5.
- 제 8항의 갈륨 함유 박막증착용 조성물을 이용하는 갈륨 함유 박막을 형성하는 방법.A method of forming a gallium-containing thin film using the composition for gallium-containing thin film deposition of claim 8.
- 제 1항 내지 제 5항에서 선택되는 어느 한 항에 따른 갈륨 화합물을 기판 상에 증착하여 박막을 형성하는 단계를 포함하는, 갈륨 함유 박막의 제조 방법.A method for producing a gallium-containing thin film, comprising forming a thin film by depositing the gallium compound according to any one of claims 1 to 5 on a substrate.
- 제 10항에 있어서,According to clause 10,상기 박막의 제조 방법은 상기 갈륨 화합물과 인듐 전구체 및 아연 전구체 중에서 선택된 1종 이상을 기재 상에 증착하여 박막을 형성하는 단계를 포함하는, 갈륨 함유 박막의 제조 방법.The method of manufacturing a gallium-containing thin film includes forming a thin film by depositing the gallium compound and at least one selected from an indium precursor and a zinc precursor on a substrate.
- 제 10항에 있어서,According to clause 10,상기 증착은 화학 기상 증착법(CVD) 또는 원자층 증착법(ALD)에 의해 수행되는 것인, 갈륨 함유 박막의 제조 방법.A method of producing a gallium-containing thin film, wherein the deposition is performed by chemical vapor deposition (CVD) or atomic layer deposition (ALD).
- 제 10항에 있어서,According to clause 10,상기 갈륨 함유 박막은 갈륨 산화물 박막, 갈륨 박막, 갈륨 질화물 박막 또는 인듐 갈륨 아연 산화물(IGZO) 박막인, 갈륨 함유 박막의 제조 방법.The gallium-containing thin film is a gallium oxide thin film, a gallium thin film, a gallium nitride thin film, or an indium gallium zinc oxide (IGZO) thin film.
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| KR1020230147198A KR20240087536A (en) | 2022-12-12 | 2023-10-30 | Gallium compound, composition for depositing thin film comprising the same, and a process for producing the thin film using the same |
| KR10-2023-0147198 | 2023-10-30 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02134387A (en) * | 1988-11-16 | 1990-05-23 | Ube Ind Ltd | Nitrogen-containing organic gallium compound |
| US5209952A (en) * | 1989-03-09 | 1993-05-11 | Merck Patent Gesellschaft Mit Beschraenkter Haftung | Use of organometallic compounds to deposit thin films from the gas phase |
| US5675028A (en) * | 1995-08-29 | 1997-10-07 | Board Of Regents, The University Of Texas System | Bisamido azides of gallium, aluminum and indium and their use as precursors for the growth of nitride films |
| KR100191737B1 (en) * | 1996-05-01 | 1999-06-15 | 이서봉 | Process for the preparation of gallium nitride film on silicon substrate |
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2023
- 2023-10-31 WO PCT/KR2023/017095 patent/WO2024128535A1/en unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02134387A (en) * | 1988-11-16 | 1990-05-23 | Ube Ind Ltd | Nitrogen-containing organic gallium compound |
| US5209952A (en) * | 1989-03-09 | 1993-05-11 | Merck Patent Gesellschaft Mit Beschraenkter Haftung | Use of organometallic compounds to deposit thin films from the gas phase |
| US5675028A (en) * | 1995-08-29 | 1997-10-07 | Board Of Regents, The University Of Texas System | Bisamido azides of gallium, aluminum and indium and their use as precursors for the growth of nitride films |
| KR100191737B1 (en) * | 1996-05-01 | 1999-06-15 | 이서봉 | Process for the preparation of gallium nitride film on silicon substrate |
Non-Patent Citations (1)
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| STERZER E., BEYER A., NATTERMANN L., SCHORN W., SCHLECHTER K., PULZ S., SUNDERMEYER J., STOLZ W., VOLZ K.: "Novel nitrogen/gallium precursor [Ga(bdma)H2] for MOVPE", JOURNAL OF CRYSTAL GROWTH, ELSEVIER, AMSTERDAM, NL, vol. 454, 1 November 2016 (2016-11-01), AMSTERDAM, NL , pages 173 - 179, XP093181388, ISSN: 0022-0248, DOI: 10.1016/j.jcrysgro.2016.08.061 * |
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