KR20200124484A - Copper alkoxyalkylamide complexes, preparation method thereof and process for thin film formation using the same - Google Patents
Copper alkoxyalkylamide complexes, preparation method thereof and process for thin film formation using the same Download PDFInfo
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- KR20200124484A KR20200124484A KR1020190047855A KR20190047855A KR20200124484A KR 20200124484 A KR20200124484 A KR 20200124484A KR 1020190047855 A KR1020190047855 A KR 1020190047855A KR 20190047855 A KR20190047855 A KR 20190047855A KR 20200124484 A KR20200124484 A KR 20200124484A
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- South Korea
- Prior art keywords
- copper
- thin film
- alkoxyalkylamide
- compound
- formula
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- 239000010949 copper Substances 0.000 title claims abstract description 176
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 169
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 153
- 239000010409 thin film Substances 0.000 title claims abstract description 115
- 238000000034 method Methods 0.000 title claims description 31
- 230000015572 biosynthetic process Effects 0.000 title description 14
- 230000008569 process Effects 0.000 title description 7
- 238000002360 preparation method Methods 0.000 title 1
- 150000001875 compounds Chemical class 0.000 claims abstract description 81
- 238000004519 manufacturing process Methods 0.000 claims abstract description 29
- -1 salt compound Chemical class 0.000 claims description 40
- 239000000203 mixture Substances 0.000 claims description 25
- 229910052751 metal Inorganic materials 0.000 claims description 24
- 239000002184 metal Substances 0.000 claims description 24
- 125000000217 alkyl group Chemical group 0.000 claims description 18
- 238000000231 atomic layer deposition Methods 0.000 claims description 13
- 238000005229 chemical vapour deposition Methods 0.000 claims description 12
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 5
- 239000005751 Copper oxide Substances 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 150000001340 alkali metals Chemical class 0.000 claims description 5
- 229910000431 copper oxide Inorganic materials 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 48
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 46
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 24
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 23
- 239000000758 substrate Substances 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 16
- 239000000463 material Substances 0.000 description 16
- 239000002243 precursor Substances 0.000 description 16
- 239000011734 sodium Substances 0.000 description 15
- 238000003786 synthesis reaction Methods 0.000 description 13
- 238000000151 deposition Methods 0.000 description 12
- 230000008021 deposition Effects 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- 239000012691 Cu precursor Substances 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 239000003446 ligand Substances 0.000 description 9
- 239000012495 reaction gas Substances 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 239000012298 atmosphere Substances 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 239000010408 film Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 230000009257 reactivity Effects 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 229910000104 sodium hydride Inorganic materials 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 238000011109 contamination Methods 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 150000002367 halogens Chemical group 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- BUHWTEKQLOECCN-UHFFFAOYSA-N n-ethoxy-2,2-dimethylpropanamide Chemical compound CCONC(=O)C(C)(C)C BUHWTEKQLOECCN-UHFFFAOYSA-N 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 229960003280 cupric chloride Drugs 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- FJRPJTNROQXADK-UHFFFAOYSA-N n-ethoxy-2-methylpropanamide Chemical compound CCONC(=O)C(C)C FJRPJTNROQXADK-UHFFFAOYSA-N 0.000 description 3
- QEDLDUHFSQPJIX-UHFFFAOYSA-N n-methoxy-2,2-dimethylpropanamide Chemical compound CONC(=O)C(C)(C)C QEDLDUHFSQPJIX-UHFFFAOYSA-N 0.000 description 3
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 239000011112 polyethylene naphthalate Substances 0.000 description 3
- 239000004926 polymethyl methacrylate Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000012312 sodium hydride Substances 0.000 description 3
- 238000007740 vapor deposition Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 2
- JVSFQJZRHXAUGT-UHFFFAOYSA-N 2,2-dimethylpropanoyl chloride Chemical compound CC(C)(C)C(Cl)=O JVSFQJZRHXAUGT-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical class [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 239000011162 core material Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000005137 deposition process Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000004455 differential thermal analysis Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 239000004210 ether based solvent Substances 0.000 description 2
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- NUXCOKIYARRTDC-UHFFFAOYSA-N o-ethylhydroxylamine;hydron;chloride Chemical compound Cl.CCON NUXCOKIYARRTDC-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- DEDZSLCZHWTGOR-UHFFFAOYSA-N propylcyclohexane Chemical compound CCCC1CCCCC1 DEDZSLCZHWTGOR-UHFFFAOYSA-N 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- PZHIWRCQKBBTOW-UHFFFAOYSA-N 1-ethoxybutane Chemical compound CCCCOCC PZHIWRCQKBBTOW-UHFFFAOYSA-N 0.000 description 1
- HYFLWBNQFMXCPA-UHFFFAOYSA-N 1-ethyl-2-methylbenzene Chemical compound CCC1=CC=CC=C1C HYFLWBNQFMXCPA-UHFFFAOYSA-N 0.000 description 1
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 description 1
- DGMOBVGABMBZSB-UHFFFAOYSA-N 2-methylpropanoyl chloride Chemical compound CC(C)C(Cl)=O DGMOBVGABMBZSB-UHFFFAOYSA-N 0.000 description 1
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- 229910005540 GaP Inorganic materials 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 229910000673 Indium arsenide Inorganic materials 0.000 description 1
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910003811 SiGeC Inorganic materials 0.000 description 1
- 229910000577 Silicon-germanium Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- DOIHHHHNLGDDRE-UHFFFAOYSA-N azanide;copper;copper(1+) Chemical group [NH2-].[Cu].[Cu].[Cu+] DOIHHHHNLGDDRE-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 1
- XKLVLDXNZDIDKQ-UHFFFAOYSA-N butylhydrazine Chemical group CCCCNN XKLVLDXNZDIDKQ-UHFFFAOYSA-N 0.000 description 1
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
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- 238000000576 coating method Methods 0.000 description 1
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- WCCJDBZJUYKDBF-UHFFFAOYSA-N copper silicon Chemical compound [Si].[Cu] WCCJDBZJUYKDBF-UHFFFAOYSA-N 0.000 description 1
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- 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
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- XNXVOSBNFZWHBV-UHFFFAOYSA-N hydron;o-methylhydroxylamine;chloride Chemical compound Cl.CON XNXVOSBNFZWHBV-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- RPQDHPTXJYYUPQ-UHFFFAOYSA-N indium arsenide Chemical compound [In]#[As] RPQDHPTXJYYUPQ-UHFFFAOYSA-N 0.000 description 1
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- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- AHADSRNLHOHMQK-UHFFFAOYSA-N methylidenecopper Chemical compound [Cu].[C] AHADSRNLHOHMQK-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 229910003465 moissanite Inorganic materials 0.000 description 1
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 1
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
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- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
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- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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- C23C16/45523—Pulsed gas flow or change of composition over time
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Abstract
Description
본 발명은 신규한 구리 알콕시알킬아미드 화합물에 관한 것으로서, 보다 상세하게는 열적 안정성과 휘발성이 개선되고 낮은 온도에서 쉽게 양질의 구리 박막의 제조가 가능한 구리 알콕시알킬아미드 화합물 및 이의 제조방법, 그리고 이를 이용하여 구리 함유 박막을 제조하는 방법 및 제조된 구리 함유 박막에 관한 것이다.The present invention relates to a novel copper alkoxyalkylamide compound, and more particularly, a copper alkoxyalkylamide compound with improved thermal stability and volatility, and capable of easily manufacturing a high-quality copper thin film at a low temperature, and a method for preparing the same, and using the same The present invention relates to a method for preparing a copper-containing thin film and the prepared copper-containing thin film.
최근, 전자 디바이스의 패턴 형성에 필요한 공정 수의 저감이 가능하고, 대량생산, 저비용화를 달성 가능한 배선·전극막의 형성법으로서 스크린 인쇄나 잉크젯법을 응용하여 배선 패턴을 형성하는 프린티드 일렉트로닉스 디바이스 기술의 발전에 따라, 기술의 핵심 재료 중의 하나로서 금속 배선용 재료의 연구가 활발하게 이루어지고 있다. Recently, as a method of forming wiring and electrode films capable of reducing the number of steps required for pattern formation of electronic devices and achieving mass production and cost reduction, the technology of printed electronics devices that applies screen printing or inkjet method to form wiring patterns. With the development, research on materials for metal wiring as one of the core materials of technology has been actively conducted.
일반적으로 사용되는 반도체 소자의 배선재료는 전기저항도가 낮고, electromigration에 대한 내성이 우수한 텅스텐(W), 알루미늄(Al), 구리(Cu), 은(Ag), 금(Au) 등을 사용할 수 있는데, 그 중에서도 구리 금속은 전기저항도가 ~1.676μΩ㎝으로 전기저항도가 ~6μΩ㎝인 텅스텐(W)이나 ~2.7μΩ㎝ 의 전기저항도를 갖는 Al 등의 배선재료에 비해 전기저항도가 월등히 낮기 때문에 신호전달속도의 향상이 요구되는 반도체 소자의 제조공정에 있어 구리 배선이 향후 핵심기술로 부각되고 있다.The wiring materials of semiconductor devices generally used can be made of tungsten (W), aluminum (Al), copper (Cu), silver (Ag), gold (Au), etc., which have low electrical resistance and excellent resistance to electromigration. Among them, copper metal has electrical resistivity of ~1.676μΩcm and electrical resistivity compared to wiring materials such as tungsten (W), which has an electrical resistivity of ~6μΩcm, or Al, which has an electrical resistance of ~2.7μΩcm. Because it is extremely low, copper wiring is emerging as a core technology in the future in the manufacturing process of semiconductor devices that require an improvement in signal transmission speed.
한편, 반도체 소자의 배선용 뿐 아니라 최근에는 태양전지 광흡수층으로 구리 질화물의 가능성이 주목받으면서 이에 관련된 구리 전구물질을 필요로 하고 있는 실정이다. On the other hand, as the possibility of copper nitride as a light absorbing layer for solar cells as well as for wiring of semiconductor devices has recently attracted attention, there is a need for a copper precursor material related thereto.
박막 제조기술 중 금속유기물화학증착법(metal organic chemical vapor deposition: MOCVD)은 제조되는 막의 층 덮힘이 우수하고 기질에 대한 선택 증착이 가능하기 때문에 구리 박막의 제조에 가장 각광 받고 있는 공정이다. 이러한 MOCVD를 박막 제작에 효과적으로 적용하기 위해서는, 우선적으로 우수한 특성을 갖는 전구물질의 확보가 중요하므로 전구물질의 개발과 특성의 이해가 필수적이다. MOCVD용 전구물질이 되기 위한 조건으로, 증기압이 충분히 높아야 하고, 기화시키기 위해 가열하는 동안 열적으로 충분히 안정하면서도, 또한 비교적 낮은 기질 온도, 예를 들면 기화 온도보다 높은 온도에서 분해하여 원하는 물질로 증착하는 온도 특성이 있어야 한다.Among the thin film manufacturing technologies, metal organic chemical vapor deposition (MOCVD) is the most popular process for manufacturing copper thin films because it has excellent layer coverage and selective deposition on a substrate. In order to effectively apply such MOCVD to thin film fabrication, it is first important to secure a precursor material having excellent properties, and therefore it is essential to develop a precursor material and understand its properties. Conditions for becoming a precursor for MOCVD, vapor pressure must be high enough, thermally stable enough during heating to vaporize, and decompose at a relatively low substrate temperature, e.g. higher than the vaporization temperature, to deposit a desired material. Must have temperature characteristics.
구리의 MOCVD용 전구물질로서 구리의 산화 상태에 따라 1가 및 2가의 유기구리 화합물이 있다. 1가 유기구리의 전구물질로는 플루오르화 베타디케톤 리간드와 중성 리간드 (L)로 이루어진 (hfac)CuL 화합물 (여기서 hfac는 1,1,1,5,5,5-헥사플루오로-2,4-펜탄디오나토 음이온임)이 대표적이며, 열 안정성이 충분치 못하고 구리박막에 탄소와 플루오르의 오염이 발생한다고 알려져 있다..As a precursor for MOCVD of copper, there are monovalent and divalent organocopper compounds depending on the oxidation state of copper. The precursor of monovalent organocopper is a (hfac)CuL compound consisting of a fluorinated betadiketone ligand and a neutral ligand (L) (where hfac is 1,1,1,5,5,5-hexafluoro-2, 4-pentanedionato anion) is typical, and it is known that the thermal stability is insufficient and contamination of carbon and fluorine occurs in the copper thin film.
한편, 열적 안정성이 취약한 구리1가 전구물질과는 달리 구리2가 전구물질들은 열정안정성이 매우 우수한데, 대표적인 구리2가 전구물질로는 베타디케토산염 및 베타케토이민염 구리 화합물에 관한 연구가 가장 많이 수행되었다. 그러나 열분해를 통해 순수한 구리 박막을 얻으려면 그 증착 온도가 매우 높아야 할 뿐만 아니라 박막 내에 탄소 오염이 심각하게 일어나는 문제점이 있다. 이외에 알콕사이드 리간드를 이용한 2가 유기구리의 전구물질에 관한 연구도 이루어지고 있는데 대표적인 예로서 미국의 버지니아 폴리텍의 데이비스(Davis) 그룹에서 Cu(OCH2CH2NMe2)2 화합물을 이용하여 구리 박막을 증착시켰으나 제조한 구리 박막이 상당량 탄소와 산소로 오염되었음을 확인하였다. 또한 최근 대만의 치(Chi) 그룹에서는 플루오르화 아미노알콕사이드를 리간드로 이용하는 2가 유기구리의 화합물 [Cu(OCCF3R1CH2NHR2)2]을 사용하여 비교적 순수한 구리 박막을 증착시켰으나, 플루오르화 아미노알콕사이드 리간드로 인해 박막 내에 플루오르에 의한 오염이 일어나는 문제점이 있다.On the other hand, unlike copper monovalent precursors, which are weak in thermal stability, copper divalent precursors have excellent thermal stability. As representative copper divalent precursors, studies on beta-diketoate and beta-ketoimine salt copper compounds Most performed. However, in order to obtain a pure copper thin film through pyrolysis, the deposition temperature must be very high, and carbon contamination occurs seriously in the thin film. In addition, studies on precursors of divalent organocopper using alkoxide ligands are also being conducted.As a representative example, a copper thin film was formed using a Cu(OCH 2 CH 2 NMe 2 ) 2 compound from the Davis group of Virginia Polytech in the United States. Although deposited, it was confirmed that the prepared copper thin film was contaminated with carbon and oxygen in a considerable amount. In addition, the Chi group in Taiwan recently deposited a relatively pure copper thin film using a divalent organocopper compound [Cu(OCCF 3 R 1 CH 2 NHR 2 ) 2 ] using a fluorinated amino alkoxide as a ligand. There is a problem that contamination by fluorine occurs in the thin film due to the amino alkoxide ligand.
또한, 박막 증착 온도가 비교적 높기 때문에 (>300℃) 폴리이미드(polyimide)와 같은 온도에 민감한 기판 소재의 사용이 제한될 뿐 아니라, 탄소(C), 산소(O), 불소(F) 와 같은 원하지 않는 불순물이 증착되는 구리박막 내 침투하기도 한다. 더불어 이들 Cu(II) 화합물은 대부분 상온에서 고체로 존재함으로 증착공정의 재현성에 심각한 영향을 주는 precursor gas flow rate를 조절하는데 있어서 어려움이 있을 수 있었다.In addition, since the deposition temperature of the thin film is relatively high (>300℃), the use of temperature-sensitive substrate materials such as polyimide is limited, as well as carbon (C), oxygen (O), and fluorine (F). Unwanted impurities may penetrate into the deposited copper thin film. In addition, since most of these Cu(II) compounds exist as solids at room temperature, there may be difficulties in controlling the precursor gas flow rate, which seriously affects the reproducibility of the deposition process.
이에 본 발명자들은 이러한 종래의 문제점을 해결하면서 구리금속 및 구리 질화물을 형성할 수 있는 구리 전구물질의 개발이 필요한 실정임을 확인하고, 열적 안정성, 화학적 반응성, 휘발성이 우수할 뿐 아니라 구리 함유 박막 형성이 용이한 신규의 유기구리 화합물을 개발하기에 이른 것이다.Accordingly, the present inventors confirmed that it is necessary to develop a copper precursor material capable of forming copper metal and copper nitride while solving these conventional problems. As well as excellent thermal stability, chemical reactivity, and volatility, the formation of a copper-containing thin film is It came to the development of a new, easy-to-use organocopper compound.
(특허문헌 1) KR10-0704464 B1 (Patent Document 1) KR10-0704464 B1
(특허문헌 2) KR10-2011-0064153 A1 (Patent Document 2) KR10-2011-0064153 A1
본 발명은 상기와 같은 문제점을 해결하기 위한 것으로서, 열적 안정성과 휘발성이 개선되고, 낮은 온도에서 쉽게 양질의 구리 함유 박막의 제조가 가능한 신규한 구리 알콕시알킬아미드 화합물을 제공하는 것을 목적으로 한다.An object of the present invention is to provide a novel copper alkoxyalkylamide compound capable of improving thermal stability and volatility, and easily producing a high-quality copper-containing thin film at a low temperature in order to solve the above problems.
본 발명의 다른 목적은 구리 알콕시알킬아미드 화합물을 제조하는 방법을 제공하는 것을 목적으로 한다.Another object of the present invention is to provide a method for preparing a copper alkoxyalkylamide compound.
본 발명의 다른 목적은 상기 구리 알콕시알킬아미드 화합물을 이용하여 구리 함유 박막을 제조하는 방법을 제공하는 것을 목적으로 한다.Another object of the present invention is to provide a method for producing a copper-containing thin film using the copper alkoxyalkylamide compound.
상기 목적을 달성하기 위하여, 본 발명은 하기 화학식 1로 표시되는 구리 알콕시알킬아미드 화합물을 제공한다.In order to achieve the above object, the present invention provides a copper alkoxyalkylamide compound represented by the following formula (1).
[화학식 1][Formula 1]
(상기 화학식 1에서, (In Formula 1,
R1 및 R2는 각각 독립적으로 C1 내지 C10의 선형 또는 분지형 알킬기이다.)R 1 and R 2 are each independently a C1 to C10 linear or branched alkyl group.)
본 발명의 일 예에 따른 상기 화학식 1의 구리 알콕시알킬아미드 화합물은, 바람직하게 R1은 C3 내지 C8의 분지형 알킬이고, R2는 C1 내지 C4의 선형 알킬인 것일 수 있다.In the copper alkoxyalkylamide compound of Formula 1 according to an example of the present invention, preferably R 1 may be a C3 to C8 branched alkyl, and R 2 may be a C1 to C4 linear alkyl.
구체적으로 본 발명의 일 예에 따른 상기 화학식 1의 구리 알콕시알킬아미드 화합물은 하기 화합물로부터 선택될 수 있으나, 이에 한정이 되는 것은 아니다.Specifically, the copper alkoxyalkylamide compound of Formula 1 according to an exemplary embodiment of the present invention may be selected from the following compounds, but is not limited thereto.
또한, 본 발명은 하기 화학식 2로 표시되는 N-알콕시알킬아미드 금속염 화합물과 하기 화학식 3으로 표시되는 구리 할라이드 화합물을 반응시켜 하기 화학식 1의 구리 알콕시알킬아미드 화합물을 제조하는 방법을 제공한다.In addition, the present invention provides a method of preparing a copper alkoxyalkylamide compound represented by the following formula (1) by reacting an N-alkoxyalkylamide metal salt compound represented by the following formula (2) with a copper halide compound represented by the following formula (3).
[화학식 1][Formula 1]
[화학식 2][Formula 2]
[화학식 3][Formula 3]
CuXCuX 22
(상기 화학식 1 내지 3에서, (In Formulas 1 to 3,
R1 및 R2는 각각 독립적으로 C1 내지 C10의 선형 또는 분지형 알킬기이며,R 1 and R 2 are each independently a C1 to C10 linear or branched alkyl group,
Z는 알칼리 금속이며,Z is an alkali metal,
X는 할로젠이다.)X is halogen.)
또한 본 발명은 하기 화학식1로 표시되는 구리 알콕시알킬아미드 화합물을 포함하는 구리 함유 박막형성용 조성물을 제공한다.In addition, the present invention provides a composition for forming a copper-containing thin film comprising a copper alkoxyalkylamide compound represented by the following formula (1).
[화학식 1][Formula 1]
(상기 화학식 1에서, (In Formula 1,
R1 및 R2는 각각 독립적으로 C1 내지 C10의 선형 또는 분지형 알킬기이다.)R 1 and R 2 are each independently a C1 to C10 linear or branched alkyl group.)
또한, 본 발명은 상기 화학식 1의 구리 알콕시알킬아미드 화합물을 이용하여 구리 함유 박막을 제조하는 방법을 제공한다.In addition, the present invention provides a method of preparing a copper-containing thin film using the copper alkoxyalkylamide compound of Formula 1 above.
본 발명의 일 예에 따른 구리 함유 박막을 제조하는 방법은 화학기상증착법(CVD) 또는 원자층증착법(ALD)에 의해 수행될 수 있다.A method of manufacturing a copper-containing thin film according to an example of the present invention may be performed by chemical vapor deposition (CVD) or atomic layer deposition (ALD).
본 발명의 일 예에 따른 구리 함유 박막을 제조하는 방법에 있어, 상기 구리 함유 박막은 구리 금속 박막, 구리 산화물 박막, 구리 질화물 박막 및 구리 산질화물 박막 등 일 수 있다.In the method of manufacturing a copper-containing thin film according to an example of the present invention, the copper-containing thin film may be a copper metal thin film, a copper oxide thin film, a copper nitride thin film, and a copper oxynitride thin film.
구체적으로 본 발명의 일 예에 따른 구리 함유 박막을 제조하는 방법에 있어, 상기 구리 함유 박막은 구리 질화물 박막일 수 있다.Specifically, in the method of manufacturing a copper-containing thin film according to an example of the present invention, the copper-containing thin film may be a copper nitride thin film.
본 발명에 따른 구리 알콕시알킬아미드 화합물은 열적 안정성과 휘발성이 우수한 특성을 가진다.The copper alkoxyalkylamide compound according to the present invention has excellent thermal stability and volatility.
또한 본 발명에 따른 구리 알콕시알킬아미드 화합물은 화학적 반응성이 우수하여 고품질의 구리 함유 박막, 특히 구리 금속 박막, 구리 산화물 박막, 구리 질화물 박막 또는 구리 산질화물 박막 등을 제조할 수 있다. In addition, since the copper alkoxyalkylamide compound according to the present invention has excellent chemical reactivity, a high-quality copper-containing thin film, in particular, a copper metal thin film, a copper oxide thin film, a copper nitride thin film, or a copper oxynitride thin film can be prepared.
또한 본 발명에 따른 구리 알콕시알킬아미드 화합물을 이용하여 제조된 구리 함유 박막은 인쇄회로기판 또는 태양전지 광흡수층의 소재로 사용될 수 있다.In addition, the copper-containing thin film prepared by using the copper alkoxyalkylamide compound according to the present invention may be used as a material for a printed circuit board or a solar cell light absorption layer.
도 1은 실시예 1에서 제조한 구리알콕시알킬아미드 화합물의 열중량/시차열분석(TG/DTA)을 나타낸 그래프이다.
도 2은 실시예 2에서 제조한 구리알콕시알킬아미드 화합물의 열중량/시차열분석(TG/DTA)을 나타낸 그래프이다.
도 3은 실시예 2에서 제조한 구리알콕시알킬아미드 화합물의 결정구조를 분석하여 나타낸 그림이다.1 is a graph showing thermogravimetric/differential thermal analysis (TG/DTA) of a copper alkoxyalkylamide compound prepared in Example 1. FIG.
2 is a graph showing thermogravimetric/differential thermal analysis (TG/DTA) of a copper alkoxyalkylamide compound prepared in Example 2.
3 is a diagram showing the analysis of the crystal structure of the copper alkoxyalkylamide compound prepared in Example 2.
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. If there are no other definitions in the technical and scientific terms used at this time, they have the meanings commonly understood by those of ordinary skill in the technical field to which this invention belongs, and the following description will unnecessarily obscure the subject matter of the present invention. Description of possible known functions and configurations will be omitted.
본 발명은 N-알콕시알킬아미드 리간드가 킬레이트 형태로 결합된 유기구리화합물로, 보다 상세하게는 하기 화학식 1로 표시되는 구리 알콕시알킬아미드 화합물에 관한 것이다.The present invention relates to an organocopper compound in which an N-alkoxyalkylamide ligand is bonded in a chelate form, and more particularly, to a copper alkoxyalkylamide compound represented by the following formula (1).
[화학식 1][Formula 1]
(상기 화학식 1에서, (In Formula 1,
R1 및 R2는 각각 독립적으로 C1 내지 C10의 선형 또는 분지형 알킬기이다.)R 1 and R 2 are each independently a C1 to C10 linear or branched alkyl group.)
본 발명의 일 예에 따른 구리 알콕시알킬아미드 화합물은 상기 화학식 1에서, 바람직하게, 상기 R1 및 R2은 각각 독립적으로 C1 내지 C8의 선형 또는 분지형 알킬기일 수 있으며, 보다 바람직하게는 R1은 C3 내지 C8의 분지형 알킬기이고 R2는 C1 내지 C4의 선형 알킬일 수 있다.The copper alkoxyalkylamide compound according to an embodiment of the present invention is in Formula 1, preferably, R 1 and R 2 may each independently be a C1 to C8 linear or branched alkyl group, and more preferably R 1 Is a C3 to C8 branched alkyl group and R 2 may be a C1 to C4 linear alkyl.
본 발명의 일 구현예에서 상기 구리 알콕시알킬아미드 화합물은 하기 화합물로부터 선택될 수 있으나, 이에 한정이 되는 것은 아니다.In one embodiment of the present invention, the copper alkoxyalkylamide compound may be selected from the following compounds, but is not limited thereto.
상기 화학식 1로 표시되는 구리 알콕시알킬아미드 화합물은 신규한 유기 구리 전구체 화합물로 금속이온인 2가의 구리와 강하게 결합될 수 있는 킬레이팅(chelating) 리간드인 N-알콕시알킬아미드 화합물을 도입함으로써 열적 안정성이 우수하고 휘발성이 개선된 특성을 가진다. 이는 N-알콕시알킬아미드 리간드의 선형 및 분지형 알킬 작용기가 분자 간 상호인력을 감소시킬 뿐 아니라 분자 간 패킹성(packing)을 방해하는 작용을 하기 때문이다. The copper alkoxyalkylamide compound represented by Formula 1 is a novel organic copper precursor compound, and thermal stability is achieved by introducing an N-alkoxyalkylamide compound, a chelating ligand that can be strongly bonded to divalent copper as a metal ion. It has excellent and improved volatility characteristics. This is because the linear and branched alkyl functional groups of the N-alkoxyalkylamide ligand not only reduce the interaction force between molecules, but also act to hinder packing between molecules.
구체적으로, 상기 화학식 1의 구리 알콕시알킬아미드 화합물은 두 개의 N-알콕시알킬아미드 리간드가 한 개의 구리2가이온에 4배위함으로써 구리 이온의 배위수를 충족할 뿐만 아니라 알파탄소 위치에 있는 치환된 알킬기와 아미드(amide)기의 산소원자에 치환된 알킬기가 분자 간 상호인력을 효과적으로 감소시켜 증기압을 높여줌과 동시에 알킬작용기들의 회전운동으로 분자 간 패킹성(packing)을 방해하여 녹는점을 떨어뜨리는 작용을 함으로써 높은 열적 안정성과 휘발성이 개선된 특성을 가질 수 있다. 또한, 이를 이용하여 박막을 제조할 경우 박막의 성장속도가 매우 우수하고, 비교적 낮은 온도에서 박막을 제조할 수 있는 장점이 있기 때문에 종래의 구리 전구체보다 화학증착 또는 원자층증착용 유기구리전구체로 보다 바람직한 특성을 보여줄 수 있다. Specifically, the copper alkoxyalkylamide compound of Formula 1 meets the coordination number of copper ions by four-coordinated two N-alkoxyalkylamide ligands to one copper divalent ion, as well as a substituted alkyl group at the alpha carbon position. The alkyl group substituted with the oxygen atom of the and amide group effectively reduces the mutual attraction between the molecules to increase the vapor pressure, and at the same time, the rotational motion of the alkyl functional groups interferes with the packing between molecules, thereby lowering the melting point. As a result, high thermal stability and volatility can be improved. In addition, when a thin film is manufactured using this, the growth rate of the thin film is very excellent, and since it has the advantage of being able to manufacture a thin film at a relatively low temperature, it is more preferable as an organic copper precursor for chemical vapor deposition or atomic layer deposition than a conventional copper precursor. Can show characteristics.
또한, 본 발명은 하기 화학식 2로 표시되는 N-알콕시알킬아미드 금속염 화합물과 하기 화학식 3으로 표시되는 구리 할라이드 화합물을 반응시켜 하기 화학식 1의 구리 알콕시알킬아미드 화합물을 제조하는 방법을 제공한다.In addition, the present invention provides a method of preparing a copper alkoxyalkylamide compound represented by the following formula (1) by reacting an N-alkoxyalkylamide metal salt compound represented by the following formula (2) with a copper halide compound represented by the following formula (3).
[화학식 1][Formula 1]
[화학식 2][Formula 2]
[화학식 3][Formula 3]
CuXCuX 22
(상기 화학식 1 내지 3에서, (In Formulas 1 to 3,
R1 및 R2는 각각 독립적으로 C1 내지 C10의 선형 또는 분지형 알킬기이며,R 1 and R 2 are each independently a C1 to C10 linear or branched alkyl group,
Z는 알칼리 금속이며,Z is an alkali metal,
X는 할로젠이다.)X is halogen.)
본 발명의 일 실시예에 따른 구리 알콕시알킬아미드 화합물의 제조방법은, 하기 반응식 1로 나타낼 수 있다.A method for preparing a copper alkoxyalkylamide compound according to an embodiment of the present invention may be represented by the following Scheme 1.
[반응식 1][Scheme 1]
(상기 반응식 1에서,(In the above Scheme 1,
R1 및 R2는 각각 독립적으로 C1 내지 C10 의 선형 또는 분지형 알킬기이고,R 1 and R 2 are each independently a C1 to C10 linear or branched alkyl group,
Z는 알칼리 금속이며,Z is an alkali metal,
X는 할로겐이다.)X is halogen.)
본 발명의 일 실시예에 따른 구리 알콕시알킬아미드 화합물의 제조방법에 있어서, 상기 Z는 1족 알칼리금속으로 예를 들어 리튬, 나트륨, 칼륨, 루비듐, 세슘일 수 있고, 상기 X는 7족 할로겐 원소로 예를 들어 불소, 염소, 브롬, 요오드일 수 있다.In the method for producing a copper alkoxyalkylamide compound according to an embodiment of the present invention, Z is a Group 1 alkali metal, for example, lithium, sodium, potassium, rubidium, cesium, and X is a Group 7 halogen element For example, it may be fluorine, chlorine, bromine, and iodine.
본 발명의 일 실시예에 따른 구리 전구체의 제조방법에 있어서, 상기 화학식 3의 구리 할라이드 화합물과 화학식 2의 N-알콕시알킬아마이드 금속염 화합물은 1 : 2 내지 1 : 3의 몰비, 바람직하게는 1 : 2 내지 1 : 2.5의 몰비로 사용될 수 있다. In the method for preparing a copper precursor according to an embodiment of the present invention, the copper halide compound of Formula 3 and the N-alkoxyalkylamide metal salt compound of Formula 2 are in a molar ratio of 1:2 to 1:3, preferably 1: It can be used in a molar ratio of 2 to 1: 2.5.
상기 화학식 2의 N-알콕시알킬아마이드 금속염 화합물과 화학식 3의 구리 할라이드 화합물의 반응[반응식 1]은 용매 하에서 이루어질 수 있다. 상기 반응에 사용되는 용매는 통상의 유기용매이면 모두 가능하며, 일예로 알칸계 용매, 방향족 용매, 에테르계 용매 등에서 선택될 수 있으며, 구체적으로 헥산(Hexane), 디에틸에테르(diethyl ether), 톨루엔(toluene), 테트라하이드로퓨란(THF) 등을 사용할 수 있고, 바람직하게는 테트라하이드로퓨란(THF)를 사용할 수 있다.The reaction of the N-alkoxyalkylamide metal salt compound of Formula 2 and the copper halide compound of Formula 3 [Scheme 1] may be performed in a solvent. The solvent used in the reaction may be any conventional organic solvent, and may be selected from an alkane-based solvent, an aromatic solvent, an ether-based solvent, and the like, and specifically, hexane, diethyl ether, and toluene. (toluene), tetrahydrofuran (THF), etc. can be used, preferably tetrahydrofuran (THF) can be used.
반응온도는 통상의 유기합성에서 사용되는 온도에서 사용가능하나, 반응물질 및 출발물질의 양에 따라 달라질 수 있으며, 바람직하게 반응식 1의 반응은 실온(room temperature, rt) 내지 100℃에서 수행될 수 있고, HPLC 또는 NMR 등을 통하여 출발물질이 완전히 소모됨을 확인한 후 반응을 완결시키도록 한다. 반응이 완결되면 추출과정 후 감압 하에서 용매를 증류시킨 후 컬럼 크로마토그래피, 재결정 또는 승화 등의 통상적인 방법을 통하여 목적물을 분리 정제할 수도 있다.The reaction temperature can be used at the temperature used in normal organic synthesis, but may vary depending on the amount of reactants and starting materials, and preferably the reaction of Scheme 1 can be carried out at room temperature (rt) to 100°C. In addition, after confirming that the starting material is completely consumed through HPLC or NMR, the reaction is completed. When the reaction is complete, the solvent may be distilled under reduced pressure after the extraction process, and then the target product may be separated and purified through a conventional method such as column chromatography, recrystallization or sublimation.
또한, 상기 반응은 질소, 아르곤 등의 비활성 기체 분위기 하에서 수행될 수 있다.In addition, the reaction may be carried out in an inert gas atmosphere such as nitrogen or argon.
상기 반응으로 제조되는 본 발명의 화학식 1의 구리 알콕시알킬아미드 화합물은 상온에서 초록색 고체 또는 액체일 수 있으며, 열적으로 안정하고 우수한 휘발성 및 높은 반응성을 가진다.The copper alkoxyalkylamide compound of Formula 1 of the present invention prepared by the above reaction may be a green solid or liquid at room temperature, and is thermally stable and has excellent volatility and high reactivity.
이하, 본 발명에 따른 구리 알콕시알킬아미드 화합물을 포함하는 구리 함유 박막형성용 조성물 및 상기 구리 알콕시알킬아미드 화합물을 이용한 구리 함유 박막의 제조방법에 대하여 설명한다.Hereinafter, a composition for forming a copper-containing thin film comprising a copper alkoxyalkylamide compound according to the present invention and a method for producing a copper-containing thin film using the copper alkoxyalkylamide compound will be described.
본 발명의 일 실시예에 따른 구리 함유 박막형성용 조성물은 하기 화학식1의 구리 알콕시알킬아미드 화합물을 포함하며, 본 발명의 조성물 내 상기 구리 알콕시알킬아미드 화합물의 사용량은 박막의 성막조건 또는 박막의 두께 및 특성 등을 고려하여 당업자가 인식할 수 있는 범위 내로 포함될 수 있음은 물론이다.The composition for forming a copper-containing thin film according to an embodiment of the present invention comprises a copper alkoxyalkylamide compound of the following formula (1), and the amount of the copper alkoxyalkylamide compound in the composition of the present invention is determined by the conditions for forming the thin film or the thickness of the thin film. It goes without saying that it may be included within the range recognized by those skilled in the art in consideration of characteristics and the like.
일 예로, 상기 구리 함유 박막형성용 조성물은 상기 구리 알콕시알킬아미드 화합물을 0.01 내지 2 M의 몰농도로 포함할 수 있다. 이때, 상기 구리 함유 박막형성용 조성물은 펜탄, 헥산, 헵탄, 옥탄, 데칸, 도데칸, 에틸시클로헥산, 프로필시클로헥산, 벤젠, 톨루엔, 에틸벤젠, 크실렌, 메시틸렌, 디에틸벤젠, 에틸 톨루엔 등의 탄화수소계 용매; 메탄올, 에탄올, 프로판올, 이소프로판올, 부탄올, 이소부탄올 등의 알콜계 용매; 디에틸에테르, 디프로필에테르, 디부틸에테르, 부틸에틸에테르, 테트라하이드로퓨란 등의 에테르계 용매; 메틸 부틸레이트, 에틸부틸레이트, 프로필프로피오네이트 등의 에스테르계 용매;에서 선택되는 하나 또는 둘 이상의 혼합유기용매를 포함하는 것일 수 있다.For example, the composition for forming a copper-containing thin film may include the copper alkoxyalkylamide compound at a molar concentration of 0.01 to 2 M. At this time, the composition for forming a thin film containing copper may include pentane, hexane, heptane, octane, decane, dodecane, ethylcyclohexane, propylcyclohexane, benzene, toluene, ethylbenzene, xylene, mesitylene, diethylbenzene, ethyl toluene, etc. Hydrocarbon solvents; Alcohol solvents such as methanol, ethanol, propanol, isopropanol, butanol and isobutanol; Ether solvents such as diethyl ether, dipropyl ether, dibutyl ether, butyl ethyl ether, and tetrahydrofuran; It may include one or more mixed organic solvents selected from; ester solvents such as methyl butyrate, ethyl butyrate, and propylpropionate.
본 발명의 일 실시예에 따른 구리 함유 박막형성용 조성물은 통상적인 용액공정을 통한 박막증착 용도로 사용되는 것일 수 있다. The composition for forming a copper-containing thin film according to an embodiment of the present invention may be used for thin film deposition through a conventional solution process .
본 발명의 일 실시예에 따른 구리 함유 박막형성용 조성물은 상기 화학식1의 구리 알콕시알킬아미드 화합물을 포함함에 따라 높은 휘발성 및 반응성으로 고밀도의 구리 함유 박막을 제공할 수 있다. Since the composition for forming a copper-containing thin film according to an embodiment of the present invention includes the copper alkoxyalkylamide compound of Formula 1, a high-density copper-containing thin film can be provided with high volatility and reactivity.
상세하게, 상기 구리 함유 박막형성용 조성물은 구리 함유 박막을 성장시키는 경우, 낮은 온도에서 쉽게 박막이 제조될 수 있으며, 박막 성장속도(Growth rate)가 좋은 장점이 있다. 즉, 상기 구리 함유 박막형성용 조성물은 본 발명의 구리 알콕시알킬아미드 화합물을 포함함에 따라 구리 함유 박막을 제조 시, 높은 증기압 및 반응성을 가지고 지속적인 가온 공정 시에도 자발적으로 분해되거나 다른 물질과 반응하는 등의 부반응을 일으키지 않아 용이하게 양질의 구리 함유 박막이 제조될 수 있다.Specifically, the composition for forming a copper-containing thin film has an advantage in that when a copper-containing thin film is grown, a thin film can be easily manufactured at a low temperature, and a thin film growth rate is good. That is, since the composition for forming a copper-containing thin film contains the copper alkoxyalkylamide compound of the present invention, it has high vapor pressure and reactivity, and spontaneously decomposes or reacts with other materials even during a continuous heating process. Since it does not cause side reactions, a high-quality copper-containing thin film can be easily manufactured.
또한, 본 발명은 상기 화학식 1로 표시되는 구리 알콕시알킬아미드 화합물을 이용하여 구리 함유 박막을 제조하는 방법 및 이로부터 제조된 구리 함유 박막을 제공한다. In addition, the present invention provides a method for preparing a copper-containing thin film using the copper alkoxyalkylamide compound represented by Chemical Formula 1, and a copper-containing thin film prepared therefrom.
본 발명의 구리 함유 박막은 상기 화학식 1의 구리 알콕시알킬아마이드 화합물을 전구체로 포함하는 구리 함유 박막형성용 조성물을 이용하여 제조된다. 비한정적인 일예로 구리 금속 박막, 구리 산화물 박막, 구리 질화물 박막, 구리 산질화물(oxynitride) 박막, 구리 탄소질화물 박막 또는 구리 규소질화물 박막일 수 있다. 보닥 구체적인 일예로, 상기 박막은 반도체 배선용 전도성 구리 금속막 또는 구리 나이트라이드막(Cu3N) 일 수 있다.The copper-containing thin film of the present invention is prepared by using a composition for forming a copper-containing thin film comprising the copper alkoxyalkylamide compound of Formula 1 as a precursor. As a non-limiting example, a copper metal thin film, a copper oxide thin film, a copper nitride thin film, a copper oxynitride thin film, a copper carbon nitride thin film, or a copper silicon nitride thin film may be used. As a specific example, the thin film may be a conductive copper metal film or a copper nitride film (Cu 3 N) for semiconductor wiring.
본 발명의 구리 함유 박막의 제조방법은 상온에서 액체 혹은 녹는점이 낮은 고체이며 휘발성이 높고 열적 안정성이 우수한 상기 화학식 1의 구리 알콕시알킬아미드 화합물을 전구체로 포함하는 본 발명의 구리 함유 박막형성용 조성물을 이용함으로써 취급이 용이하고, 다양한 박막의 제조가 가능할 뿐만 아니라 고밀도 및 고순도의 구리 함유 박막을 제조할 수 있다. 나아가 본 발명의 제조방법으로 제조된 구리 함유 박막은 내구성 및 전기적 특성이 우수하고 단차피복성이 우수하다.The method for producing a copper-containing thin film of the present invention uses the composition for forming a copper-containing thin film of the present invention containing the copper alkoxyalkylamide compound of Formula 1 as a precursor, which is a liquid at room temperature or a solid with a low melting point and has high volatility and excellent thermal stability. By doing so, it is easy to handle, and it is possible to manufacture various thin films, as well as to produce a copper-containing thin film having high density and high purity. Furthermore, the copper-containing thin film manufactured by the method of the present invention has excellent durability and electrical properties, and excellent step coverage.
본 발명의 구리 함유 박막의 제조방법은 본 기술분야에서 당업자가 인식할 수 있는 범위 내에서 가능한 방법이라면 모두 가능하나, 바람직하게 원자층증착법(ALD), 화학기상증착법(CVD), 유기금속화학기상증착법(MOCVD), 저압기상증착법(LPCVD), 플라즈마강화기상증착법(PECVD) 또는 플라즈마강화원자층증착법(PEALD)으로 수행될 수 있다.The manufacturing method of the copper-containing thin film of the present invention can be any method within the range that can be recognized by those skilled in the art, but preferably, atomic layer deposition (ALD), chemical vapor deposition (CVD), organometallic chemical vapor phase It may be performed by a vapor deposition method (MOCVD), a low pressure vapor deposition method (LPCVD), a plasma enhanced vapor deposition method (PECVD), or a plasma enhanced atomic layer deposition method (PEALD).
본 발명의 구리 함유 박막의 제조방법은 구체적으로 The manufacturing method of the copper-containing thin film of the present invention is specifically
a) 챔버 내에 장착된 기판의 온도를 80 내지 400℃로 유지하는 단계;a) maintaining the temperature of the substrate mounted in the chamber at 80 to 400°C;
b) 수송가스와 상기 구리 함유 박막형성용 조성물을 주입하는 단계; 및 b) injecting a transport gas and the composition for forming a thin film containing copper; And
c) 반응가스를 주입하여 상기 기판 상에 구리 함유 박막을 증착시키는 단계;를 포함할 수 있으며, 구리 함유 박막의 두께에 따라 b) 및 c)단계를 수 회 반복할 수 있다.c) injecting a reaction gas to deposit a copper-containing thin film on the substrate, and steps b) and c) may be repeated several times depending on the thickness of the copper-containing thin film.
본 발명의 일 실시예에 따른 구리 함유 박막의 제조방법은 목적하는 박막의 구조 또는 열적 특성에 따라 증착 조건이 조절될 수 있으며, 본 발명의 일 실시예에 따른 증착 조건으로는 구리 알콕시알킬아마이드 화합물을 포함하는 금속 함유 박막형성용 조성물의 투입 유량, 반응가스, 운반 가스의 투입 유량, 압력, RF 파워, 기판 온도 등이 예시될 수 있으며, 이러한 증착 조건의 비한정적인 일예로는 구리 함유 박막형성용 조성물의 투입 유량은 10 내지 1000 cc/min, 운반가스는 10 내지 1000 cc/min, 반응가스의 유량은 1 내지 1000 cc/min, 압력은 0.5 내지 10 torr, RF 파워는 200 내지 1000 W 및 기판 온도는 80 내지 400 ℃ 범위, 바람직하게는 200 내지 400 ℃ 범위에서 조절될 수 있으나 이에 한정이 있는 것은 아니다.In the method of manufacturing a copper-containing thin film according to an embodiment of the present invention, the deposition conditions may be adjusted according to the structure or thermal characteristics of the desired thin film, and the deposition conditions according to an embodiment of the present invention include a copper alkoxyalkylamide compound. The input flow rate, the reaction gas, the input flow rate of the carrier gas, the pressure, the RF power, the substrate temperature, etc. of the composition for forming a metal-containing thin film including, as a non-limiting example of such deposition conditions, a composition for forming a copper-containing thin film The input flow rate is 10 to 1000 cc/min, the carrier gas is 10 to 1000 cc/min, the flow rate of the reaction gas is 1 to 1000 cc/min, the pressure is 0.5 to 10 torr, the RF power is 200 to 1000 W and the substrate temperature May be adjusted in the range of 80 to 400 °C, preferably 200 to 400 °C, but is not limited thereto.
본 발명의 구리 함유 박막의 제조방법에서 사용되는 반응가스는 한정이 있는 것은 아니나 제조하고자 하는 구리 함유 박막을 고려하여 통상적으로 금속 전구체와 함께 사용되는 가스이면 무방하며, 구체적인 일예로, 함산소 가스는 산소(O2), 오존(O3), 증류수(H2O) 또는 과산화수소(H2O2) 등일 수 있으며, 함질소 가스는 일산화질소(NO), 아산화질소(N2O), 이산화질소(NO2), 암모니아(NH3), 질소(N2), 하이드라진(N2H4) 또는 터셔리부틸하이드라진(C4H12N2) 등의 하이드라진 유도체일 수 있고, 함탄소 가스는 일산화탄소(CO), 이산화탄소(CO2), C1 내지 C12 포화 또는 불포화 탄화수소 등일 수 있으나 이는 일 예시일 뿐 이에 제한받지 않는다. 또한 상기 반응가스는 질소(N2), 헬륨(He) 또는 아르곤(Ar) 등의 불활성 가스와 혼합하여 사용될 수도 있으며 기타 반응가스로서 수소가 사용될 수도 있다.The reaction gas used in the method for producing a copper-containing thin film of the present invention is not limited, but any gas that is usually used with a metal precursor in consideration of the copper-containing thin film to be produced may be used. As a specific example, the oxygen-containing gas is It may be oxygen (O 2 ), ozone (O 3 ), distilled water (H 2 O) or hydrogen peroxide (H 2 O 2 ), and the nitrogen-containing gas is nitrogen monoxide (NO), nitrous oxide (N 2 O), nitrogen dioxide ( NO 2 ), ammonia (NH 3 ), nitrogen (N 2 ), hydrazine (N 2 H 4 ) or tertiary butyl hydrazine (C 4 H 12 N 2 ) may be a hydrazine derivative such as, and the carbon-containing gas is carbon monoxide ( CO), carbon dioxide (CO 2 ), C1 to C12 saturated or unsaturated hydrocarbons, etc., but this is only an example and is not limited thereto. In addition, the reaction gas may be mixed with an inert gas such as nitrogen (N 2 ), helium (He) or argon (Ar), and hydrogen may be used as other reaction gas.
본 발명의 일 예에 따른 구리 알콕시알킬아미드 화합물은 우수한 휘발성은 물론 높은 온도 중에도 쉽게 분해되지 않으며, 기화 후에도 안정적인 증기 상태를 유지할 수 있어 상술된 증착방법에 효과적일 수 있다.The copper alkoxyalkylamide compound according to an exemplary embodiment of the present invention has excellent volatility, is not easily decomposed even at high temperatures, and can maintain a stable vapor state even after vaporization, so it may be effective in the above-described deposition method.
일예로, 유기금속화학기상증착법(MOCVD)은 기판이 위치하는 증착 영역에 구리 알콕시알킬아마이드 화합물을 주입하는 단계 및 증착 영역에 반응 가스를 주입하는 단계를 포함하는 증착 과정을 포함하고 각 단계들은 동시적으로 또는 순차적으로 진행되며, 구리 알콕시알킬아미드 화합물과 반응가스는 반응하여 기판 상에서 금속이 함유된 박막을 형성한다. For example, organometallic chemical vapor deposition (MOCVD) includes a deposition process including injecting a copper alkoxyalkylamide compound into a deposition area where a substrate is located and a reactive gas into the deposition area, and each of the steps is simultaneously performed. Proceeding separately or sequentially, the copper alkoxyalkylamide compound and the reaction gas react to form a thin film containing metal on the substrate.
일예로, 원자층 증착법(ALD)은 기판이 위치하는 증착 영역에 구리 알콕시알킬아마이드 화합물을 주입하는 단계, 증착 영역에서 구리 알콕시알킬아마이드 화합물을 흡착시키는 단계 및 증착 영역에 반응가스를 주입하는 단계와 박막을 형성하는 단계가 순차적으로 수행되며, 상기의 각 단계가 1회 진행되면 구리가 함유된 박막 단층이 증착된다. 각 단계의 반복적인 과정을 거쳐 원하는 두께의 구리 함유 박막을 증착할 수 있다.For example, in the atomic layer deposition (ALD), injecting a copper alkoxyalkylamide compound into a deposition region where a substrate is located, adsorbing a copper alkoxyalkylamide compound in the deposition region, and injecting a reaction gas into the deposition region. The steps of forming a thin film are sequentially performed, and when each of the above steps is performed once, a single layer of a thin film containing copper is deposited. It is possible to deposit a copper-containing thin film of a desired thickness through an iterative process of each step.
상기 기판은 통상의 기판이라면 제한되지 않으며, 이의 비한정적인 일 예로는 Si, Ge, SiGe, GaP, GaAs, SiC, SiGeC, InAs 및 InP중 하나 이상의 반도체 재료를 포함하는 기판, SOI(Silicon On Insulator)기판, 석영 기판 또는 디스플레이용 유리 기판 등의 강성 기판이거나, 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 기판일 수 있다.The substrate is not limited as long as it is a conventional substrate, and a non-limiting example thereof is a substrate including one or more semiconductor materials of Si, Ge, SiGe, GaP, GaAs, SiC, SiGeC, InAs, and InP, a silicon on insulator (SOI). ) Or a rigid substrate such as a substrate, a quartz substrate, or a glass substrate for a display, or polyimide, polyethylene terephthalate (PET), polyethylene naphthalate (PEN, PolyEthylene Naphthalate), polymethylmethacrylate (PMMA, Poly Methyl MethAcrylate), polycarbonate (PC, PolyCarbonate), polyethersulfone (PES), polyester (Polyester) may be a flexible plastic substrate.
또한 상기 구리 함유 박막은 상기 기판에 직접 박막을 형성하는 것 뿐 아니라, 상기 기판과 상기 구리 함유 박막 사이에 다수의 도전층, 유전층 또는 절연층 등을 포함할 수 있다.In addition, the copper-containing thin film may include a plurality of conductive layers, dielectric layers, or insulating layers between the substrate and the copper-containing thin film, as well as directly forming a thin film on the substrate.
상기 구리 함유 박막형성용 조성물 및 구리 함유 박막의 제조방법을 이용하여 우수한 단차피복성을 가질 수 있으며, 밀도가 높은 고순도의 구리 함유 박막을 제조할 수 있다.The composition for forming a copper-containing thin film and the method for producing a copper-containing thin film may have excellent step coverage, and a high-purity copper-containing thin film having a high density may be prepared.
즉, 본 발명의 일 실시예에 따른 구리 함유 박막을 제조하는 방법에 따르면, ALD 공정 또는 CVD 공정 등을 통해 용이하게 목적하는 고밀도의 높은 유전상수를 갖는 고유전 박막 재료를 공급함에 따라 반도체 소자의 배선, 트랜지스터의 게이트 절연막, 커패시터의 유전막 또는 전자부품의 코팅막 형성 등에 다양하게 활용될 수 있다.That is, according to the method of manufacturing a copper-containing thin film according to an embodiment of the present invention, a high dielectric constant thin film material having a high density and high dielectric constant is easily supplied through an ALD process or a CVD process. It can be used in various ways such as forming a wiring, a gate insulating film of a transistor, a dielectric film of a capacitor, or a coating film of an electronic component.
일예로, 상기 구리 알콕시알킬아미드 화합물을 사용하여 구리 금속 박막을 제조하는 경우, 상기 구리 알콕시알킬아미드 화합물이 충분한 휘발성을 보일뿐 아니라 반응성이 좋아 비교적 쉽게 구리 금속으로 환원되므로 고순도의 전도성 구리 금속 박막을 제조할 수 있다. 따라서 상기 구리 알콕시알킬아미드 화합물을 사용하여 구리 금속 박막으로 금속 배선, 전극 또는 회로로서 응용이 가능하고, 바람직하게는 반도체 배선용 금속막으로서 매우 적합하여 인쇄회로기판에 사용될 수 있다.For example, in the case of manufacturing a copper metal thin film using the copper alkoxyalkylamide compound, the copper alkoxyalkylamide compound exhibits sufficient volatility and is relatively easily reduced to copper metal due to its high reactivity, thus forming a high-purity conductive copper metal thin film. Can be manufactured. Therefore, the copper alkoxyalkylamide compound can be used as a copper metal thin film as a metal wiring, an electrode, or a circuit, and is preferably very suitable as a metal film for semiconductor wiring and can be used for a printed circuit board.
또한, 본 발명의 구리 알콕시알킬아미드 화합물을 이용하여 제조된 구리 함유 박막은 태양전지용 소재에 사용될 수 있다.In addition, the copper-containing thin film prepared by using the copper alkoxyalkylamide compound of the present invention can be used for a solar cell material.
구체적인 일예로, 상기 구리 함유 박막의 제조방법으로 상기 화학식 1의 구리 알콕시알킬아미드 화합물을 사용하여 용이하게 구리 질화물을 형성할 수 있으며, 제조되는 구리 질화물이 구리 나이트라이드(Cu3N)인 경우 태양광 적용에 적절한 밴드갭(Band gap, Bg), 내결함성 및 캐리어(carrier) 수송능력이 뛰어나 질화물 태양전지 소재로 사용될 수 있고, 바람직하게는 태양전지 광흡수층에 사용될 수 있다.As a specific example, the copper-containing thin film may be easily formed by using the copper alkoxyalkylamide compound of Chemical Formula 1, and the prepared copper nitride is copper nitride (Cu 3 N). It can be used as a material for a nitride solar cell because of its excellent band gap (Bg), fault resistance, and carrier transport ability suitable for light application, and preferably used for a light absorption layer of a solar cell.
이하 본 발명을 실시예를 통해 상세히 설명하나, 이들은 본 발명을 보다 상세하게 설명하기 위한 것으로, 본 발명의 권리범위가 하기의 실시예에 의해 한정되는 것은 아니다. Hereinafter, the present invention will be described in detail through examples, but these are for explaining the present invention in more detail, and the scope of the present invention is not limited by the following examples.
이하 본 발명에 따른 구리 알콕시알킬아미드 화합물의 실시예는 글로브 박스 또는 슐랭크 관(schlenk line)을 이용하여 비활성 아르곤 또는 질소 분위기 하에서 수행 하였으며, 수득된 표제 화합물의 구조분석은 단결정 X-선 회절분석을 통해 측정되었다. 이 때 사용한 분석기기는 Bruker SMART APEX Ⅱ 로서, 타켓은 Mo 이고 X-선 소스는 파장 0.71073 Å의 MoKα radiation으로 측정되었다.Hereinafter, examples of the copper alkoxyalkylamide compound according to the present invention were carried out in an inert argon or nitrogen atmosphere using a glove box or a Schlenk line, and the structural analysis of the obtained title compound was performed by single crystal X-ray diffraction analysis. It was measured through. The analyzer used at this time was Bruker SMART APEX II, the target was Mo and the X-ray source was measured with MoKα radiation with a wavelength of 0.71073 Å.
또한 상기 구리 알콕시알킬아미드 화합물의 열적 안정성 및 휘발성과 분해온도를 측정하기 위해, 열특성 분석을 위하여 TG/DTA 분석을 실시하였다. 상기 TG/DTA법은 수득된 표제 화합물을 10mg 정도를 취하여 알루미나 시료용기에 넣은 후10℃/분의 속도로 800℃까지 가온시키면서, 1.5 bar/분의 압력으로 질소 기체 주입 하에 측정되었다.In addition, in order to measure the thermal stability, volatility and decomposition temperature of the copper alkoxyalkylamide compound, TG/DTA analysis was performed for thermal property analysis. In the TG/DTA method, about 10 mg of the obtained title compound was taken and placed in an alumina sample container, while heating to 800° C. at a rate of 10° C./min, and nitrogen gas injection at a pressure of 1.5 bar/min.
[합성예 1] 소듐[N-에톡시-2-메틸프로판아미드], (Na[empa])의 합성[Synthesis Example 1] Synthesis of sodium [N-ethoxy-2-methylpropanamide], (Na [empa])
단계 1: N-에톡시-2-메틸프로판아미드(empaH) 합성Step 1: Synthesis of N-ethoxy-2-methylpropanamide (empaH)
둥근 바닥 플라스크(Round-bottom flask)에 O-에틸하이드록실아민 하이드로클로라이드(O-ethylhydroxylamine hydrochloride) (6.15 g, 0.063 mol) 와 테트라하이드로퓨란(THF) 150 mL를 첨가한 후, 트라이에틸아민(triethylamine) (25 mL, 0.18 mol)을 넣고 상온에서 30분간 교반하였다. 이후, 0°C 분위기에서, 아이소부틸릴 클로라이드(isobutyryl chloride) (6.39 g, 0.060 mol)를 천천히 적가하고, 상온으로 천천히 온도를 올린 뒤, 70℃에서 12시간동안 교반하였다. 12시간 후 얼음물로 반응을 종결시키고, 에틸아세테이트(EA)를 이용하여 여과하고 감압농축한 뒤, 에틸아세테이트(EA)로 세척(wash) 하였다. 세척 후 얻어진 혼합물을 감압 증류(110 ℃/10-1Torr)로 정제하여 투명한 결정의 N-에톡시-2-메틸프로판아미드(empaH) (5.20 g, 수율67%)를 얻었다.After adding O-ethylhydroxylamine hydrochloride (6.15 g, 0.063 mol) and 150 mL of tetrahydrofuran (THF) to a round-bottom flask, triethylamine ) (25 mL, 0.18 mol) was added and stirred at room temperature for 30 minutes. Thereafter, in an atmosphere of 0 °C, isobutyryl chloride (6.39 g, 0.060 mol) was slowly added dropwise, and the temperature was slowly raised to room temperature, followed by stirring at 70 °C for 12 hours. After 12 hours, the reaction was terminated with ice water, filtered with ethyl acetate (EA), concentrated under reduced pressure, and washed with ethyl acetate (EA). After washing, the obtained mixture was purified by distillation under reduced pressure (110° C./10 -1 Torr) to obtain transparent crystals of N-ethoxy-2-methylpropanamide (empaH) (5.20 g, yield 67%).
1H-NMR (C6D6, 400 MHz) δ 1.14 (m, 9H, COC(CH3)2, OCH2CH3), 2.62 (br, 1H, COCH), 3.95 (q, 2H, OCH2CH3), 11.33 (br, 1H , NH) ppm. 1 H-NMR (C 6 D 6 , 400 MHz) δ 1.14 (m, 9H, COC(CH 3 ) 2, OCH 2 CH 3 ), 2.62 (br, 1H, COCH), 3.95 (q, 2H, OCH 2 CH 3 ), 11.33 (br, 1H, NH) ppm.
13C-NMR (C6D6, 100 MHz) δ 13.6 (OCH2CH3), 19.6 (COCH(CH3)2), 32.1 (COCH), 71.5 (OCH2CH3), 175.5 (COCH(CH3)2) ppm. 13 C-NMR (C 6 D 6 , 100 MHz) δ 13.6 (OCH 2 CH 3 ), 19.6 (COCH(CH 3 ) 2 ), 32.1 (COCH), 71.5 (OCH 2 CH 3 ), 175.5 (COCH(CH 3 ) 2 ) ppm.
FT-IR (ν/cm-1) : 3196s, 2985s, 2935m, 2878m, 1661s, 1517m, 1470m, 1384m, 1236w, 1158w, 1122w, 1096m, 1050s, 987w, 952w, 880w, 850w, 802w, 668w.FT-IR (ν/cm -1 ): 3196s, 2985s, 2935m, 2878m, 1661s, 1517m, 1470m, 1384m, 1236w, 1158w, 1122w, 1096m, 1050s, 987w, 952w, 880w, 850w, 802w, 668w.
Anal. Calcd for C6H13NO2 : C, 54.94; H, 9.99; N, 10.68. Found: C, 54.45; H, 9.87; N, 10.42.Anal. Calcd for C 6 H 13 NO 2 : C, 54.94; H, 9.99; N, 10.68. Found: C, 54.45; H, 9.87; N, 10.42.
단계 2: 소듐[N-에톡시-2-메틸프로판아미드], Na[empa] 합성Step 2: Synthesis of sodium [N-ethoxy-2-methylpropanamide], Na [empa]
수소화나트륨(NaH) (2.4g, 0.1mol)을 질소 분위기 하에서 테트라하이드로퓨란(THF) 150mL에 혼합시킨 후 -15℃의 저온 분위기를 형성한 뒤 단계 1의 N-에톡시-2-메틸프로판아미드(emdaH) (13.1g, 0.1mol)을 첨가하였다. 상기 혼합액을 -15℃에서 상온으로 천천히 온도를 올린 뒤, 1시간동안 반응을 진행하였다. 반응종료 후 여과하여 미반응 고체를 제거하고 얻어진 용액을 건조하여 옅은 노란색 고체인 소듐[N-에톡시-2-메틸프로판아미드], Na[empa]를 수득하였다(9.2g, 수율 60.4%).After mixing sodium hydride (NaH) (2.4 g, 0.1 mol) in 150 mL of tetrahydrofuran (THF) under a nitrogen atmosphere, forming a low-temperature atmosphere at -15° C., and N-ethoxy-2-methylpropanamide in step 1 (emdaH) (13.1 g, 0.1 mol) was added. After slowly raising the temperature of the mixture from -15°C to room temperature, the reaction was carried out for 1 hour. After the reaction was completed, unreacted solid was removed by filtration, and the resulting solution was dried to obtain sodium [N-ethoxy-2-methylpropanamide] and Na [empa] as pale yellow solids (9.2 g, yield 60.4%).
[합성예 2] 소듐[N-에톡시-2,2-다이메틸프로판아미드], (Na[edpa])의 합성[Synthesis Example 2] Synthesis of sodium [N-ethoxy-2,2-dimethylpropanamide], (Na[edpa])
단계 1: N-에톡시-2,2-다이메틸프로판아미드(edpaH) 합성Step 1: Synthesis of N-ethoxy-2,2-dimethylpropanamide (edpaH)
둥근 바닥 플라스크(Round-bottom flask)에 O-에틸하이드록실아민 하이드로클로라이드(O-Ethylhydroxylamine hydrochloride) (6.15 g, 0.063 mol) 와 테트라하이드로퓨란(THF) 150 mL를 첨가한 후, 트라이에틸아민(triethylamine) (25 mL, 0.18 mol)을 넣고 상온에서 30분간 교반하였다. 이후, 0°C 분위기에서, 피바로일 클로라이드(Pivaloylchloride) (7.24 g, 0.060 mol)를 천천히 적가하고, 상온으로 천천히 온도를 올린 뒤, 70℃에서 12시간동안 교반하였다. 12시간 후 얼음물로 반응을 종결시키고, 에틸아세테이트(EA)를 이용하여 여과하고 감압농축한 뒤, 에틸아세테이트(EA)로 세척(wash) 하였다. 세척 후 얻어진 혼합물을 감압 증류(120 ℃/10-1Torr)로 정제하여 투명한 결정의 N-에톡시-2,2-다이메틸프로판아미드(edpaH) (6.01 g, 수율69%)를 얻었다.After adding O-Ethylhydroxylamine hydrochloride (6.15 g, 0.063 mol) and 150 mL of tetrahydrofuran (THF) to a round-bottom flask, triethylamine ) (25 mL, 0.18 mol) was added and stirred at room temperature for 30 minutes. Thereafter, in an atmosphere of 0 ° C., pivaloyl chloride (7.24 g, 0.060 mol) was slowly added dropwise, and the temperature was slowly raised to room temperature, followed by stirring at 70 °C for 12 hours. After 12 hours, the reaction was terminated with ice water, filtered with ethyl acetate (EA), concentrated under reduced pressure, and washed with ethyl acetate (EA). After washing, the obtained mixture was purified by vacuum distillation (120° C./10 -1 Torr) to obtain transparent crystals of N-ethoxy-2,2-dimethylpropanamide (edpaH) (6.01 g, yield 69%).
1H-NMR (C6D6, 400 MHz) δ 1.10 (s, 9 H, COC(CH3)3), 1.16(t, 3 H, -CH3), 3.84 (q, 2 H, OCH2-), 8.20 (s, 1 H , NH). 1 H-NMR (C 6 D 6 , 400 MHz) δ 1.10 (s, 9 H, COC(CH 3 ) 3 ), 1.16(t, 3 H, -CH 3 ), 3.84 (q, 2 H, OCH 2 -), 8.20 (s, 1 H, NH).
13C-NMR (C6D6, 100 MHz) δ 13.7 (-CH3), 27.4 (COC(CH3)3), 37.9 (COC(CH3)3), 71.4 (OCH2-), 176.0 (COC(CH3)3). 13 C-NMR (C 6 D 6 , 100 MHz) δ 13.7 (-CH 3 ), 27.4 (COC(CH 3 ) 3 ), 37.9 (COC(CH 3 ) 3 ), 71.4 (OCH 2 -), 176.0 ( COC(CH 3 ) 3 ).
FT-IR (ν/cm-1) : 3226s, 2979s, 1652s, 1506s, 1483s, 1462m, 1399w, 1386w, 1368w, 1294w, 1229w, 1159w, 1123w, 1091w, 1057s, 1029m, 1009m, 933m, 863w, 812w, 598w.FT-IR (ν/cm -1 ): 3226s, 2979s, 1652s, 1506s, 1483s, 1462m, 1399w, 1386w, 1368w, 1294w, 1229w, 1159w, 1123w, 1091w, 1057s, 1029m, 1009m, 933m, 863w, 812w , 598w.
EA(Anal. Calcd for C7H15NO2 : C, 57.90; H, 10.41; N, 9.65. Found: C, 57.88; H, 10.38; N, 9.61)EA (Anal.Calcd for C 7 H 15 NO 2 : C, 57.90; H, 10.41; N, 9.65.Found: C, 57.88; H, 10.38; N, 9.61)
단계 2: 소듐[N-에톡시-2,2-다이메틸프로판아미드], (Na[edpa]) 합성Step 2: Synthesis of sodium[N-ethoxy-2,2-dimethylpropanamide], (Na[edpa])
수소화나트륨(NaH) (2.4g, 0.1 mol)을 질소 분위기 하에서 테트라하이드로퓨란(THF) 150mL에 혼합시킨 후 -15℃의 저온 분위기를 형성한 뒤 단계 1의 N-에톡시-2,2-다이메틸프로판아미드(edpaH) (14.5g, 0.5mol)을 첨가하였다. 상기 혼합액을 -15℃에서 1시간동안 교반한 뒤 환류 콘덴서를 이용하여 24시간동안 환류교반 반응을 진행하였다. 반응종료 후 여과하여 얻어진 용액을 감한 뒤 미반응 고체와 용매 및 휘발성 부반응 물질을 제거하여 펜탄(pentane)으로 첨가한 후 추출된 물질을 건조하여 옅은 노란색 고체인 소듐[N-에톡시-2,2-다이메틸프로판아미드], Na[edpa]를 수득하였다(6.5g, 수율 60.4%).After mixing sodium hydride (NaH) (2.4 g, 0.1 mol) in 150 mL of tetrahydrofuran (THF) under a nitrogen atmosphere, forming a low-temperature atmosphere at -15° C., N-ethoxy-2,2-di Methylpropanamide (edpaH) (14.5 g, 0.5 mol) was added. The mixture was stirred at -15°C for 1 hour and then refluxed and stirred for 24 hours using a reflux condenser. After the reaction was completed, the solution obtained by filtration was subtracted, unreacted solids, solvents, and volatile side reactions were removed, added with pentane, and the extracted material was dried to form sodium [N-ethoxy-2,2]. -Dimethylpropanamide], Na [edpa] was obtained (6.5 g, yield 60.4%).
[합성예 3] 소듐[N-메톡시-2,2-다이메틸프로판아미드], (Na[mdpa])의 합성[Synthesis Example 3] Synthesis of sodium [N-methoxy-2,2-dimethylpropanamide], (Na[mdpa])
단계 1: N-메톡시-2,2-다이메틸프로판아미드(mdpaH) 합성Step 1: Synthesis of N-methoxy-2,2-dimethylpropanamide (mdpaH)
둥근 바닥 플라스크(Round-bottom flask)에 O-메틸하이드록실아민 하이드로클로라이드(O-Methylhydroxylamine hydrochloride) (5.26 g, 0.063 mol) 와 테트라하이드로퓨란(THF) 150 mL를 첨가한 후, 트라이에틸아민(triethylamine) (25 mL, 0.18 mol)을 넣고 상온에서 30분간 교반하였다. 이후, 0°C 분위기에서, 피바로일 클로라이드(Pivaloylchloride) (7.24 g, 0.060 mol)를 천천히 적가하고, 상온으로 천천히 온도를 올린 뒤, 70℃에서 12시간동안 교반하였다. 12시간 후 얼음물로 반응을 종결시키고, 에틸아세테이트(EA)를 이용하여 여과하고 감압농축한 뒤, 에틸아세테이트(EA)로 세척(wash) 하였다. 세척 후 얻어진 혼합물을 감압 증류(70 ℃/10-1Torr)로 정제하여 투명한 액체의 N-메톡시-2,2-다이메틸프로판아미드(mdpaH) (5.35 g, 수율68%)를 얻었다.After adding 150 mL of O-Methylhydroxylamine hydrochloride (5.26 g, 0.063 mol) and tetrahydrofuran (THF) to a round-bottom flask, triethylamine ) (25 mL, 0.18 mol) was added and stirred at room temperature for 30 minutes. Thereafter, in an atmosphere of 0 ° C., pivaloyl chloride (7.24 g, 0.060 mol) was slowly added dropwise, and the temperature was slowly raised to room temperature, followed by stirring at 70 °C for 12 hours. After 12 hours, the reaction was terminated with ice water, filtered with ethyl acetate (EA), concentrated under reduced pressure, and washed with ethyl acetate (EA). The mixture obtained after washing was purified by distillation under reduced pressure (70° C./10 -1 Torr) to obtain a transparent liquid N-methoxy-2,2-dimethylpropanamide (mdpaH) (5.35 g, yield 68%).
1H-NMR (C6D6, 400 MHz) δ 1.09 (s, 9H, COC(CH3)3), 3.59 (s, 3H, OCH3), 9.30 (s, 1H , NH). 1 H-NMR (C 6 D 6 , 400 MHz) δ 1.09 (s, 9H, COC(CH 3 ) 3 ), 3.59 (s, 3H, OCH 3 ), 9.30 (s, 1H, NH).
13C-NMR (C6D6, 100 MHz) δ 27.2(COC(CH3)3), 37.8(COC(CH3)3), 63.5(OCH3), 175.8(COC(CH3)3). 13 C-NMR (C 6 D 6 , 100 MHz) δ 27.2 (COC(CH 3 ) 3 ), 37.8 (COC(CH 3 ) 3 ), 63.5 (OCH 3 ), 175.8 (COC(CH 3 ) 3 ).
FT-IR (ν/cm-1) : 3228s, 2967s, 2873m, 2813m, 2813w, 1653s, 1506s, 1482s, 1440w, 1400m, 1368m , 1294w, 1226m, 1060s, 1021m, 941m, 917m, 811w, 622w, 586w.FT-IR (ν/cm -1 ): 3228s, 2967s, 2873m, 2813m, 2813w, 1653s, 1506s, 1482s, 1440w, 1400m, 1368m, 1294w, 1226m, 1060s, 1021m, 941m, 917m, 811w, 622w, 586w .
Anal. Calcd for C6H13NO2 : C, 54.94; H, 9.99; N, 10.68. Found: C, 54.45; H, 9.87; N, 10.42.Anal. Calcd for C 6 H 13 NO 2 : C, 54.94; H, 9.99; N, 10.68. Found: C, 54.45; H, 9.87; N, 10.42.
단계 2: 소듐[N-메톡시-2,2-다이메틸프로판아미드], Na[mdpa] 합성Step 2: Synthesis of sodium [N-methoxy-2,2-dimethylpropanamide], Na[mdpa]
수소화나트륨(NaH) (2.4g, 0.1mol)을 질소 분위기 하에서 테트라하이드로퓨란(THF) 150mL에 혼합시킨 후 -15℃의 저온 분위기를 형성한 뒤 단계 1의 N-메톡시-2,2-다이메틸프로판아미드(mpdaH) (13.1g, 0.1mol)을 첨가하였다. 상기 혼합액을 -15℃에서 상온으로 천천히 온도를 올린 뒤, 1시간동안 반응을 진행하였다. 반응종료 후 여과하여 미반응 고체를 제거하고 얻어진 용액을 건조하여 옅은 노란색 고체인 소듐[N-메톡시-2,2-다이메틸프로판아미드], Na[mdpa]를 수득하였다(9.2g, 수율 60.4%).After mixing sodium hydride (NaH) (2.4 g, 0.1 mol) in 150 mL of tetrahydrofuran (THF) under a nitrogen atmosphere, forming a low-temperature atmosphere at -15° C., and then N-methoxy-2,2-di Methylpropanamide (mpdaH) (13.1 g, 0.1 mol) was added. After slowly raising the temperature of the mixture from -15°C to room temperature, the reaction was carried out for 1 hour. After completion of the reaction, the unreacted solid was removed by filtration, and the resulting solution was dried to obtain sodium [N-methoxy-2,2-dimethylpropanamide] and Na[mdpa] as pale yellow solids (9.2 g, yield 60.4). %).
[실시예 1] 비스(N-에톡시-2-메틸프로판아미드)구리, Cu(empa)[Example 1] Bis (N-ethoxy-2-methylpropanamide) copper, Cu (empa) 22 의 제조Manufacture of
슈렝크 플라스크에 염화제2구리(CuCl2) (0.134g, 1.0mmol)을 50ml 테트라하이드로퓨란(THF)에 용해시킨 후, 소듐[N-에톡시-2-메틸프로판아미드](Na[mdpa]) (0.322g, 2.1 mmol)를 첨가한 뒤 12 시간 동안 교반하였다. 반응물을 여과하여 얻은 용액을 감압증류하여 부산물을 제거한 뒤 헥산(Hexane)으로 추출하였다. 추출액의 헥산(hexane)을 제거하여 표제 화합물을 얻었다(초록색 고체, 0.275 g, 수율 85.1 %).Cupric chloride (CuCl 2 ) in a Schlenk flask (0.134 g, 1.0 mmol) was dissolved in 50 ml tetrahydrofuran (THF), and sodium [N-ethoxy-2-methylpropanamide] (Na [mdpa]) (0.322 g, 2.1 mmol) was added. Stir for 12 hours. The solution obtained by filtering the reaction product was distilled under reduced pressure to remove by-products, and then extracted with hexane. Hexane from the extract was removed to obtain the title compound (green solid, 0.275 g, yield 85.1%).
상기 표제 화합물의 경우에는, 70 ℃ 부근에서 질량 감소가 일어나기 시작했으며, 110 ℃에서 180 ℃사이 52%의 질량 감소 및 360℃에서 70%의 질량 감소가 관찰되었다.In the case of the title compound, a mass decrease began to occur around 70°C, and a mass decrease of 52% between 110°C and 180°C and a mass decrease of 70% at 360°C were observed.
EA(Anal. Calcd for C12H24CuN2O4: C, 44.50; H, 7.47; N, 8.65. Found: C, 44.43; H, 7.51; N, 8.31)EA (Anal.Calcd for C 12 H 24 CuN 2 O 4 : C, 44.50; H, 7.47; N, 8.65.Found: C, 44.43; H, 7.51; N, 8.31)
Melting Point : 95 ℃Melting Point: 95 ℃
[실시예 2] 비스(N-에톡시-2,2-다이메틸프로판아미드)구리, Cu(edpa)[Example 2] Bis (N-ethoxy-2,2-dimethylpropanamide) copper, Cu (edpa) 22 의 제조Manufacture of
슈렝크 플라스크에 염화제2구리(CuCl2) (0.134g, 1.0mmol)을 테트라하이드로퓨란(THF)에 용해시킨 후, 소듐[N-에톡시-2,2-다이메틸프로판아미드](Na[edpa]) (0.351g, 2.1mmol)를 넣어 12 시간 동안 환류하였다. 반응물을 여과하여 얻은 용액을 감압 하에서 부산물을 제거한 뒤 헥산(hexane)으로 추출하였다. 추출액의 헥산(hexane)을 제거한 후 50℃/0.05mmHg 조건으로 승화하여 표제 화합물을 얻었다(초록색 고체, 0.25 g, 수율 71%). After dissolving cupric chloride (CuCl 2 ) (0.134 g, 1.0 mmol) in tetrahydrofuran (THF) in a Schlenk flask, sodium [N-ethoxy-2,2-dimethylpropanamide] (Na[ edpa]) (0.351g, 2.1mmol) was added and refluxed for 12 hours. The solution obtained by filtering the reaction product was extracted with hexane after removing by-products under reduced pressure. After removing hexane from the extract, the mixture was sublimated at 50° C./0.05 mmHg to obtain the title compound (green solid, 0.25 g, yield 71%).
상기 표제 화합물의 경우에는, 100℃ 부근에서 질량 감소가 일어나기 시작했으며, 200 ℃까지 75%의 질량 감소 및 360 ℃까지 83%의 질량 감소가 관찰되었다.In the case of the title compound, mass reduction began to occur around 100°C, and a mass reduction of 75% up to 200°C and a mass reduction of 83% up to 360°C were observed.
EA(Anal. Calcd for C14H28CuN2O4: C, 47.78; H, 8.02; N, 7.96. Found: C, 48.65; H, 8.09; N, 7.58)EA (Anal.Calcd for C14H28CuN2O4: C, 47.78; H, 8.02; N, 7.96.Found: C, 48.65; H, 8.09; N, 7.58)
Melting Point: 118 ℃Melting Point: 118 ℃
[실시예 3] 비스(N-메톡시-2,2-다이메틸프로판아미드)구리, Cu(mdpa)[Example 3] Bis (N-methoxy-2,2-dimethylpropanamide) copper, Cu (mdpa) 22 의 제조Manufacture of
슈렝크 플라스크에 염화제2구리(CuCl2) (0.134g, 1.0mmol)을 50ml 테트라하이드로퓨란(THF)에 용해시킨 후, 소듐[N-메톡시-2,2-다이메틸프로판아미드](Na[mdpa]) (0.322g, 2.1mmol)를 첨가한 뒤 12 시간 동안 교반하였다. 반응물을 여과하여 얻은 용액을 감압증류하여 부산물을 제거한 뒤 헥산(Hexane)으로 추출하였다. 추출액의 헥산(hexane)을 제거한 뒤 70℃/0.05mmHg 조건으로 승화하여 표제 화합물을 얻었다(초록색 고체, 0.12g, 수율 37%).Cupric chloride (CuCl 2 ) in a Schlenk flask (0.134 g, 1.0 mmol) was dissolved in 50 ml tetrahydrofuran (THF), and then sodium [N-methoxy-2,2-dimethylpropanamide] (Na [mdpa]) (0.322 g, 2.1 mmol) was added. After addition, the mixture was stirred for 12 hours. The solution obtained by filtering the reaction product was distilled under reduced pressure to remove by-products, and then extracted with hexane. After removing hexane from the extract, it was sublimated under conditions of 70°C/0.05mmHg to obtain the title compound (green solid, 0.12g, yield 37%).
EA(Anal. Calcd for C12H24CuN2O4: C, 44.50; H, 7.47; N, 8.65. Found: C, 44.51; H, 7.12; N, 7.16).EA (Anal. Calcd for C 12 H 24 CuN 2 O 4 : C, 44.50; H, 7.47; N, 8.65.Found: C, 44.51; H, 7.12; N, 7.16).
[실험예 1] 열특성 평가[Experimental Example 1] Evaluation of thermal properties
상기 실시예 1 내지 2에서 제조한 구리 전구체 화합물들의 기초 열특성을 분석하기 위하여 TG/DTA(Thermal gravimetric/Differential Thermal anaysis) 분석을 진행하였다. 이때 각 전구체 샘플의 무게는 약 10mg 정도를 취하여 알루미나 시료 용기에 넣은 후 10℃/min.의 승온 속도로 800℃까지 측정한 결과를 각각 도 1 및 2에 나타내었다.In order to analyze the basic thermal properties of the copper precursor compounds prepared in Examples 1 to 2, thermal gravimetric/differential thermal anaysis (TG/DTA) analysis was performed. At this time, the weight of each precursor sample was about 10 mg, put in an alumina sample container, and then measured up to 800° C. at a heating rate of 10° C./min. are shown in FIGS. 1 and 2, respectively.
도 1 및 2에서 확인할 수 있듯이 본 발명에 따른 실시예 1 내지 2의 구리 전구체 화합물들은 모두 화학기상 증착 혹은 원자층 증착에 적용하기에 충분한 휘발성을 나타냄을 보여주고 있다.As can be seen in FIGS. 1 and 2, all of the copper precursor compounds of Examples 1 to 2 according to the present invention show sufficient volatility to be applied to chemical vapor deposition or atomic layer deposition.
또한 온도에 따른 무게 감소율이 급격히 완만해지기 지각하는 온도가 전구체 화합물의 본격적인 분해가 시작하는 온도로 볼 수 있으므로, 본 발명에 따른 실시예 1 내지 2에서 합성된 구리 전구체 화합물들은 우수한 열적 안정성의 특성을 가지고 있음을 확인할 수 있었다.In addition, since the temperature at which the weight reduction rate according to the temperature is perceived to rapidly become gentle can be seen as the temperature at which the full decomposition of the precursor compound begins, the copper precursor compounds synthesized in Examples 1 to 2 according to the present invention have excellent thermal stability characteristics. It was confirmed that it has.
따라서 본 발명의 구리 알콕시알킬아미드 화합물은 열적안정성이 우수하기 때문에 화학기상증착 및 원자층증착 공정에서 적용하였을 경우 더욱 높은 온도에서 공정이 용이하고, 전구체의 열분해에 기인하는 파티클 오염이나 탄소 등의 불순물 오염이 없는 높은 순도의 구리 금속, 구리 산화물 및 구리 질화물 박막을 성장시키는데 유리한 구리 전구체로 사용될 수 있을 것으로 기대된다.Therefore, since the copper alkoxyalkylamide compound of the present invention has excellent thermal stability, it is easy to process at higher temperatures when applied in chemical vapor deposition and atomic layer deposition processes, and impurities such as particle contamination or carbon caused by thermal decomposition of the precursor. It is expected that it can be used as an advantageous copper precursor to grow thin films of high purity copper metal, copper oxide and copper nitride without contamination.
이상과 같이 본 발명에서는 특정된 사항들과 한정된 실시예 및 도면에 의해 설명되었으나 이는 본 발명의 보다 전반적인 이해를 돕기 위해서 제공된 것일 뿐, 본 발명은 상기의 실시예에 한정되는 것은 아니며, 본 발명이 속하는 분야에서 통상의 지식을 가진 자라면 이러한 기재로부터 다양한 수정 및 변형이 가능하다. As described above, the present invention has been described by specific matters and limited embodiments and drawings, but this is provided only to help a more general understanding of the present invention, and the present invention is not limited to the above embodiments, and the present invention is Those of ordinary skill in the relevant field can make various modifications and variations from this description.
따라서, 본 발명의 사상은 설명된 실시 예에 국한되어 정해져서는 아니되며, 후술하는 특허청구범위뿐 아니라 이 특허청구범위와 균등하거나 등가적 변형이 있는 모든 것들은 본 발명 사상의 범주에 속한다고 할 것이다.Therefore, the spirit of the present invention is limited to the described embodiments and should not be defined, and all things that are equivalent or equivalent to the claims as well as the claims to be described later fall within the scope of the spirit of the present invention. .
Claims (9)
[화학식 1]
(상기 화학식 1에서,
R1 및 R2는 각각 독립적으로 C1 내지 C10의 선형 또는 분지형 알킬기이다.)Copper alkoxyalkylamide compound represented by the following formula (1):
[Formula 1]
(In Formula 1,
R 1 and R 2 are each independently a C1 to C10 linear or branched alkyl group.)
상기 화학식 1에서 R1은 C3 내지 C8의 분지형 알킬이고,
R2는 C1 내지 C4의 선형 알킬인 구리 알콕시알킬아미드 화합물.The method of claim 1,
R 1 in Formula 1 is a C3 to C8 branched alkyl,
R 2 is a copper alkoxyalkylamide compound which is a C1 to C4 linear alkyl.
하기 화합물로부터 선택되는 것인 구리 알콕시알킬아미드 화합물.
A copper alkoxyalkylamide compound selected from the following compounds.
[화학식 1]
[화학식 2]
[화학식 3]
CuX 2
(상기 화학식 1 내지 3에서,
R1 및 R2는 각각 독립적으로 C1 내지 C10의 선형 또는 분지형 알킬기이며,
Z는 알칼리 금속이며,
X는 할로젠이다.)A method for preparing a copper alkoxyalkylamide compound of the following formula 1 by reacting an N-alkoxyalkylamide metal salt compound represented by the following formula (2) with a copper halide compound represented by the following formula (3):
[Formula 1]
[Formula 2]
[Formula 3]
CuX 2
(In Formulas 1 to 3,
R 1 and R 2 are each independently a C1 to C10 linear or branched alkyl group,
Z is an alkali metal,
X is halogen.)
화학기상증착법(CVD) 또는 원자층증착법(ALD)에 의해 수행되는 것인, 구리 함유 박막을 제조하는 방법.The method of claim 6,
Chemical vapor deposition (CVD) or atomic layer deposition (ALD) is a method for producing a thin film containing copper.
상기 구리 함유 박막은 구리 금속 박막, 구리 산화물 박막, 구리 질화물 박막 또는 구리 산질화물 박막인, 구리 함유 박막을 제조하는 방법.The method of claim 6,
The copper-containing thin film is a copper metal thin film, a copper oxide thin film, a copper nitride thin film, or a copper oxynitride thin film.
상기 구리 함유 박막은 구리 질화물 박막인, 구리 함유 박막을 제조하는 방법.
The method of claim 6,
The copper-containing thin film is a copper nitride thin film, a method of manufacturing a copper-containing thin film.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100704464B1 (en) | 2003-02-26 | 2007-04-10 | 한국화학연구원 | Copper aminoalkoxide complexes, preparation method thereof and process for the formation of copper thin film using the same |
| KR20110064153A (en) | 2009-12-07 | 2011-06-15 | 삼성전자주식회사 | Metallic organic precursor, method for preparing the same, and method for forming conductive metal layer or pattern |
| KR20140015404A (en) * | 2011-02-25 | 2014-02-06 | 우미코레 아게 운트 코 카게 | Metal complexes with n-aminoamidinate ligands |
| KR20170055274A (en) * | 2015-11-11 | 2017-05-19 | 한국화학연구원 | Stannum precursors, preparation method thereof and process for the formation of thin film using the same |
-
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100704464B1 (en) | 2003-02-26 | 2007-04-10 | 한국화학연구원 | Copper aminoalkoxide complexes, preparation method thereof and process for the formation of copper thin film using the same |
| KR20110064153A (en) | 2009-12-07 | 2011-06-15 | 삼성전자주식회사 | Metallic organic precursor, method for preparing the same, and method for forming conductive metal layer or pattern |
| KR20140015404A (en) * | 2011-02-25 | 2014-02-06 | 우미코레 아게 운트 코 카게 | Metal complexes with n-aminoamidinate ligands |
| KR20170055274A (en) * | 2015-11-11 | 2017-05-19 | 한국화학연구원 | Stannum precursors, preparation method thereof and process for the formation of thin film using the same |
Non-Patent Citations (1)
| Title |
|---|
| Etelka Farkas 등, Polyhedron, 1998, Vol. 17, No. 19, pp.2220-2231 * |
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