TWI374870B - Copper(i) formate complexes - Google Patents
Copper(i) formate complexes Download PDFInfo
- Publication number
- TWI374870B TWI374870B TW093138009A TW93138009A TWI374870B TW I374870 B TWI374870 B TW I374870B TW 093138009 A TW093138009 A TW 093138009A TW 93138009 A TW93138009 A TW 93138009A TW I374870 B TWI374870 B TW I374870B
- Authority
- TW
- Taiwan
- Prior art keywords
- copper
- complex
- formula
- substrate
- formate
- Prior art date
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- FSGSLHGEFPNBBN-UHFFFAOYSA-M copper(1+);formate Chemical class [Cu+].[O-]C=O FSGSLHGEFPNBBN-UHFFFAOYSA-M 0.000 title 1
- 239000010949 copper Substances 0.000 claims description 51
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 48
- 229910052802 copper Inorganic materials 0.000 claims description 48
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 36
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 32
- -1 amine alkyl Chemical group 0.000 claims description 19
- 235000019253 formic acid Nutrition 0.000 claims description 19
- HFDWIMBEIXDNQS-UHFFFAOYSA-L copper;diformate Chemical compound [Cu+2].[O-]C=O.[O-]C=O HFDWIMBEIXDNQS-UHFFFAOYSA-L 0.000 claims description 18
- 239000003446 ligand Substances 0.000 claims description 17
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 16
- 239000000758 substrate Substances 0.000 claims description 16
- 238000000151 deposition Methods 0.000 claims description 15
- 239000002131 composite material Substances 0.000 claims description 12
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 150000001336 alkenes Chemical class 0.000 claims description 6
- 239000012442 inert solvent Substances 0.000 claims description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 3
- 229910000831 Steel Inorganic materials 0.000 claims description 3
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 3
- 239000010959 steel Substances 0.000 claims description 3
- KPUPVWORBVCEOT-UHFFFAOYSA-N copper;triphenylphosphane Chemical compound [Cu].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 KPUPVWORBVCEOT-UHFFFAOYSA-N 0.000 claims 3
- 150000001345 alkine derivatives Chemical class 0.000 claims 2
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 claims 2
- YWWDBCBWQNCYNR-UHFFFAOYSA-N trimethylphosphine Chemical compound CP(C)C YWWDBCBWQNCYNR-UHFFFAOYSA-N 0.000 claims 2
- BLPGWZAQVVZJOA-UHFFFAOYSA-N 1-butyl-9h-fluorene Chemical compound C1C2=CC=CC=C2C2=C1C(CCCC)=CC=C2 BLPGWZAQVVZJOA-UHFFFAOYSA-N 0.000 claims 1
- SIJSIIFAIYLAQW-UHFFFAOYSA-N 1-tert-butyl-9h-fluorene Chemical compound C12=CC=CC=C2CC2=C1C=CC=C2C(C)(C)C SIJSIIFAIYLAQW-UHFFFAOYSA-N 0.000 claims 1
- LHQRDAIAWDPZGH-UHFFFAOYSA-N cyclohexylhydrazine Chemical compound NNC1CCCCC1 LHQRDAIAWDPZGH-UHFFFAOYSA-N 0.000 claims 1
- FWBOFUGDKHMVPI-UHFFFAOYSA-K dicopper;2-oxidopropane-1,2,3-tricarboxylate Chemical compound [Cu+2].[Cu+2].[O-]C(=O)CC([O-])(C([O-])=O)CC([O-])=O FWBOFUGDKHMVPI-UHFFFAOYSA-K 0.000 claims 1
- 150000002576 ketones Chemical class 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 claims 1
- KJAQRHMKLVGSCG-UHFFFAOYSA-N propan-2-ylhydrazine Chemical compound CC(C)NN KJAQRHMKLVGSCG-UHFFFAOYSA-N 0.000 claims 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 claims 1
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 claims 1
- IGNTWNVBGLNYDV-UHFFFAOYSA-N triisopropylphosphine Chemical compound CC(C)P(C(C)C)C(C)C IGNTWNVBGLNYDV-UHFFFAOYSA-N 0.000 claims 1
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 claims 1
- SJHCUXCOGGKFAI-UHFFFAOYSA-N tripropan-2-yl phosphite Chemical compound CC(C)OP(OC(C)C)OC(C)C SJHCUXCOGGKFAI-UHFFFAOYSA-N 0.000 claims 1
- CBIQXUBDNNXYJM-UHFFFAOYSA-N tris(2,2,2-trifluoroethyl) phosphite Chemical compound FC(F)(F)COP(OCC(F)(F)F)OCC(F)(F)F CBIQXUBDNNXYJM-UHFFFAOYSA-N 0.000 claims 1
- DAGQYUCAQQEEJD-UHFFFAOYSA-N tris(2-methylpropyl)phosphane Chemical compound CC(C)CP(CC(C)C)CC(C)C DAGQYUCAQQEEJD-UHFFFAOYSA-N 0.000 claims 1
- 239000002904 solvent Substances 0.000 description 25
- JIDMEYQIXXJQCC-UHFFFAOYSA-L copper;2,2,2-trifluoroacetate Chemical compound [Cu+2].[O-]C(=O)C(F)(F)F.[O-]C(=O)C(F)(F)F JIDMEYQIXXJQCC-UHFFFAOYSA-L 0.000 description 18
- 239000007787 solid Substances 0.000 description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- 239000007788 liquid Substances 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Natural products CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 238000000354 decomposition reaction Methods 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 230000008021 deposition Effects 0.000 description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 7
- 238000004528 spin coating Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 150000004820 halides Chemical class 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000000995 aerosol-assisted chemical vapour deposition Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002798 polar solvent Substances 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- KBMDBLCFKPRPOC-UHFFFAOYSA-N 2-bromo-3,3,3-trifluoro-2-(trifluoromethyl)propanenitrile Chemical compound FC(F)(F)C(Br)(C#N)C(F)(F)F KBMDBLCFKPRPOC-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000005749 Copper compound Substances 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
- 150000001880 copper compounds Chemical class 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- SZXCZUDYSKBGSX-UHFFFAOYSA-N copper;2-ethylhexanoic acid Chemical compound [Cu].CCCCC(CC)C(O)=O.CCCCC(CC)C(O)=O SZXCZUDYSKBGSX-UHFFFAOYSA-N 0.000 description 2
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 210000003746 feather Anatomy 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000004377 microelectronic Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- NUMQCACRALPSHD-UHFFFAOYSA-N tert-Butyl ethyl ether Natural products CCOC(C)(C)C NUMQCACRALPSHD-UHFFFAOYSA-N 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- FHUDAMLDXFJHJE-UHFFFAOYSA-N 1,1,1-trifluoropropan-2-one Chemical compound CC(=O)C(F)(F)F FHUDAMLDXFJHJE-UHFFFAOYSA-N 0.000 description 1
- JQJBQVRTSMGDJX-UHFFFAOYSA-N 1-[(2-methylpropan-2-yl)oxy]decane Chemical compound CCCCCCCCCCOC(C)(C)C JQJBQVRTSMGDJX-UHFFFAOYSA-N 0.000 description 1
- PZHIWRCQKBBTOW-UHFFFAOYSA-N 1-ethoxybutane Chemical compound CCCCOCC PZHIWRCQKBBTOW-UHFFFAOYSA-N 0.000 description 1
- CXBDYQVECUFKRK-UHFFFAOYSA-N 1-methoxybutane Chemical compound CCCCOC CXBDYQVECUFKRK-UHFFFAOYSA-N 0.000 description 1
- 241001674044 Blattodea Species 0.000 description 1
- MXJDQIWBHIXNRE-UHFFFAOYSA-B C(CC(O)(C(=O)[O-])CC(=O)[O-])(=O)[O-].[C+4].C(CC(O)(C(=O)[O-])CC(=O)[O-])(=O)[O-].C(CC(O)(C(=O)[O-])CC(=O)[O-])(=O)[O-].C(CC(O)(C(=O)[O-])CC(=O)[O-])(=O)[O-].[C+4].[C+4] Chemical compound C(CC(O)(C(=O)[O-])CC(=O)[O-])(=O)[O-].[C+4].C(CC(O)(C(=O)[O-])CC(=O)[O-])(=O)[O-].C(CC(O)(C(=O)[O-])CC(=O)[O-])(=O)[O-].C(CC(O)(C(=O)[O-])CC(=O)[O-])(=O)[O-].[C+4].[C+4] MXJDQIWBHIXNRE-UHFFFAOYSA-B 0.000 description 1
- CYPXIELOSKRPBK-UHFFFAOYSA-N CCO[PH2](OCC)OCC Chemical compound CCO[PH2](OCC)OCC CYPXIELOSKRPBK-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- CMGCAQOUARLVKY-UHFFFAOYSA-N [Cu].C(=N)N Chemical compound [Cu].C(=N)N CMGCAQOUARLVKY-UHFFFAOYSA-N 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 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
- ATZQZZAXOPPAAQ-UHFFFAOYSA-M caesium formate Chemical compound [Cs+].[O-]C=O ATZQZZAXOPPAAQ-UHFFFAOYSA-M 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000012230 colorless oil Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- LTYZGLKKXZXSEC-UHFFFAOYSA-N copper dihydride Chemical compound [CuH2] LTYZGLKKXZXSEC-UHFFFAOYSA-N 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- OUFLLVQXSGGKOV-UHFFFAOYSA-N copper ruthenium Chemical compound [Cu].[Ru].[Ru].[Ru] OUFLLVQXSGGKOV-UHFFFAOYSA-N 0.000 description 1
- GDFGBZPSSUEBJH-UHFFFAOYSA-L copper(1+);oxalate Chemical compound [Cu+].[Cu+].[O-]C(=O)C([O-])=O GDFGBZPSSUEBJH-UHFFFAOYSA-L 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- FUEIRJYWUVGJBC-UHFFFAOYSA-M copper;2-ethylhexanoate;propan-2-olate Chemical compound [Cu+2].CC(C)[O-].CCCCC(CC)C([O-])=O FUEIRJYWUVGJBC-UHFFFAOYSA-M 0.000 description 1
- LSIWWRSSSOYIMS-UHFFFAOYSA-L copper;diformate;tetrahydrate Chemical compound O.O.O.O.[Cu+2].[O-]C=O.[O-]C=O LSIWWRSSSOYIMS-UHFFFAOYSA-L 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
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- 239000003880 polar aprotic solvent Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Classifications
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/1208—Oxides, e.g. ceramics
- C23C18/1216—Metal oxides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/08—Copper compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/005—Compounds containing elements of Groups 1 or 11 of the Periodic Table without C-Metal linkages
-
- 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/5045—Complexes or chelates of phosphines with metallic compounds or metals
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/08—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of metallic material
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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Inorganic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Chemical Vapour Deposition (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
1374870 九、發明說明： 【發明所屬之技術領域】 本發明係關於甲酸銅（I)複合物。由於其經分解可沉積金 屬銅，所以銅複合物被用於微電子技術中，例如，藉由自 氣相沉積（化學蒸氣沉積法或簡稱CVD)或自溶液沉積（旋塗 法）以沉積銅導體。此種沉積法可作為銅之習知濺射法（一 種物理蒸氣沉積法、或簡稱PVD，其中物質並不會變質） 或銅晶種塗敷法之替代法，其可改良其後藉由濺射法塗敷 之銅層之沉積性及黏著性。 【先前技術】 在 The Chemistry of Metal CVD(Wiley-VCH Verlag GmbH & Co. KGaA，Weinheim, 1994, ISBN 3-527-29071-0)，第 239-302 頁中，T.T. Kodas及 M.J. Hambden-Smith說明用以 沉積銅之已知CVD法及其習知起始物之概要。尤其是β-二 酮酸銅（II)複合物、β-二酮酸銅（I)複合物、β-醯基酮亞胺 銅⑴複合物、β-二醯亞胺銅⑴複合物、環五雙烯基酮⑴複 合物及烴氧化銅。由於其安定性、處理性、有效性及價 格，所以最常使用此等二酮酸鹽，其最大的缺點為若不使 用額外還原劑，其銅產率相當低，不超過50%。例如， D.K. Sohn，S.C. Park, S.W. Kang及 B.T. Ahn在 J. Electrochem. Soc.144 (1997)，第3592-3596頁中描述另一種沉積銅之方 法，亦即旋轉塗布法或旋塗式方法，其中係塗敷含不可汽 化但是可分解之銅化合物之溶液或銅分散液至旋轉基片 上，並藉由旋轉分布，因此可沉積均句銅薄膜。 97705.doc 1374870 銅化合物或具有羧酸鹽或烷氧酸鹽之銅複合物係普遍已 知，且其亦可用以沉積金屬銅。F.A. Cotton, E.V. Dikarev 及 M.A. Terukhina在 Inorg. Chem. (2000)，第 6072-6079 頁中描述三氟醋酸銅⑴及三氟醋酸銅（II)。三氟醋酸酮（I) 可昇華，因此，原則上適於作為CVD之起始物質。E. IIjina, A. Korjeva, N. Kuzmina, S. Troyanov, K. DunaevaA L. Martynenko在 Mater. Sci. Eng. B 1 8 (1993)，第 234-236 頁 中描述揮發性三曱基醋酸銅（I)之製法及其結晶結構。 S.A.Krupoder，V.S. Danilovich, A.O. Miller及 G.G. Furii^J. Fluorine Chem. 21(1995)，第13-15頁報導揮發性雙（三氟 醋酸）銅（II)之合成法及其熱重研究。M.E. Gross在J. Electrochem. Soc. 13 8 (8) (1991)，第 2422-2426 頁中描述 (部份）氟化烴氧化銅（I)及其與（環戊二烯基）（三乙基膦基） 銅（I)及第三-丁氧化羰基銅（I)與工業上最常使用之CVD起 始物質雙（六氟乙醯基丙嗣酸）銅（II)之揮發性比較。CN 1 2 40 689A揭示藉由羧酸鹽之熱解製備極微細銅粉末之方 法。 JP 06/184 749描述藉由第三-丁氧基銅羰基物之分解製備 銅薄膜之方法。WO 01/13426 A1描述雙（2-乙基己酸）銅 (II)、（己酸2-乙酯）異丙氧化銅（II)及（己酸2-乙酯）曱氧基乙 氧化銅（II)用於銅沉積之應用。DE 41 38 722 A1揭示借助 於苄醇使四曱基庚烷二酸銅（II)蒸發之方法。EP 976 847 A2描述自雙（2-乙基己酸）銅（II)製備銅薄膜之方法。DE 39 22 233 A1描述藉由雷射照射自羧酸銅（II)製備銅導體之方 97705.doc 1374870 法。WO 01/94 291 A1 揭示 Cu(OCCF3R丨CH2NHR2)2型之銅 (II)複合物，其中R1為氫、CVC4-烷基或CVCV全氟烷基， 且112為CrCr烷基或烯烴，其亦可視需要經氟、烷 氧基或烷胺基取代；及其用於沉積銅薄膜之應用。申請案 號為DE 10325243.6(2003年6月3曰申請）之先前德國專利申 請案描述藉由使基片與甲酸銅（II)化合物及式 Ι^Ο((：Η2)η(：ΗΙ12ΝΗ2烷氧基烷基胺（其中R1為曱基或乙基， R2為氫或甲基，而η為1、2、3、或4)接觸以沉積銅層在基 片上之方法。K. Kohler，J. Eichhorn，F. Meyer 及 D. Vidovic 在 Organometallics 22. (2003)，第 4426-4432 頁報告具有快 烴或烯烴配位基之草酸二銅（I)複合物及其用於藉由旋塗法 或在溶液上喷灑以進行分解（簡稱氣溶膠協助之CVD或 AACVD)使銅自溶液内沉積之應用。 明確地說，甲酸銅（II)及藉由此等化合物之分解沉積金 屬銅之方法亦係已知。J.-K Kim，S.-K. Park及C. Lee, J.在 Korean Phys. Soc. U (5) (1999)，第 426-430頁中描述藉由 雷射引發銅沉積之方法使用甲酸銅（Π)四水合物以製備微 結構物之應用。M.-J. Mouche，J.-L. Mermet，C· Mathon及 R. Cimard 在 Adv. Sci. Technol. (Adv. Inorg. Films and Coatings) i (1995)，第 231-238 頁，及 M.-J. Mouche，L· Mermet, M. Romand及 M. Charbonnier在 Thin Solid Films 262 (1995)，第1-6頁中報告曱酸銅（II)水合物在載送氣體 中作為CVD之起始物質之應用。R. Padiyath, M. David及 S. V. Babu在Metallized Plastics 2 (1991)，第 113-120頁中描 97705.doc 1374870 述在氫電漿中自曱酸銅（Π)製備銅薄膜之方法。Κ-ραόίγβίΙι， J. Seth， S.V. Babu 及 L.J. Matienzo 在】.人卩卩1· Phys. 21 (5) (1993)，第2326-2332頁中報告在矽上沉積 銅，並藉由塗敷曱酸銅以形成矽化銅，然後在氫電漿中進 行還原反應。J.-K. Lee於 1999年 1 月在Microelectronic and
Optoelectronic Manufacturing IV (San Jose, California, USA)有關 Laser Applications之 SPIE Conference上報告藉由 經氬雷射照射自甲酸銅（Π)製備銅薄膜之方法（參閱 Proceedings SPIE-Int. Soc. Opt. Eng. 3618 (1999)，第 378-3 85)。EP 1 077 084 A2之實例24揭示藉由曱酸銅之熱分解 使銅沉積在絲光沸石上之方法。EP 368 23 1 A2描述藉由曱 酸銅（II)之熱解使銅沉積在特型樹脂物件上之方法。在US 5 141 602 A之方法中，描述藉由雷射照射分解甲酸銅（II) 以沉積銅之方法，及在JP 11/193 461A之方法中，再一次 描述藉由熱分解沉積銅之方法。
A. Keller及 F. K6r0sy在 Nature 162 (1948)，第 580-582 頁 中報告藉由曱酸銅（II)之分解所製成之曱酸銅（1)(其被稱為 CuHCOO)，且一旦加熱至105°C時，該曱酸銅（I)可分解成 銅、二氧化碳及氫。D.A. Edwards 及 R. Richards 在 J. Chem.
Soc. Dalton Trans. (1973)，第 2463-2468頁中描述在曱酸中 藉由使曱酸銅（II)與金屬銅反應以合成曱酸銅（I)之方法。 更詳細地說，已知甲酸銅（I)係呈配位基安定化複合物之型 式，通常為LnCu(HCOO)型，其中Ln為至少雙配位基 L(n=l)或（n=2、3或4)或至少單配位基之配位基。L. B. 97705.doc 1374870 上式中之X數為可等於零之數值，但是通常為至少〇1、 較佳至少0.5、更特佳至少i，且通常不超過丨〇 '較佳不超 過5、更特佳不超過2。X最佳為 式中’ η為1、2' 3或4。η較佳為2或3。 L為一種下述配位基。當η大於丨時，其互相獨立選自： -式WWp磷烷； -式（1^0)(1120)(尺3〇)?亞磷酸鹽； -式 RJ-NC胩； -式RiRksCW烯烴；或 -式R]CsCR2块烴； 其中R1、R2、R3及R4於各情況下，互相獨立為·· 氫或 具有一或20個碳原子之直鏈或分支鏈、視需要經部份或 元全氟化之烷基、胺烷基、烷氧烷基、羥烷基、膦烷基 或芳基。 此等直鏈或分支鏈烷基之實例為甲基、乙基、正-丙 基、異丙基、正_ 丁基、第二_ 丁基、異丁基、第三·丁基及 2-乙基己基、異構性戊基、己基、庚基、辛基、壬基、癸 基、十一烷基或十二烷基、及環烷基，例如，環丙基、環 丁基、環戊基、環己基、環庚基、環辛基及雙環壬基、其 亦可帶有烷基取代基。除了氫外，此等碳原子亦可帶有其 它取代基，例如，齒素取代基，特別為I。2或更多種此 等基團亦可形成閉環系（其亦可以呈不飽和性）。此種配位 基L之實例為環戊二烯基，其形式上為烯烴 97705.doc 1374870 一丙醚、二丁醚、四氫呋喃、第三-丁基曱基醚或第三丁 基乙基醚；及鹵化（特別為氯化）烷烴溶劑，例如，二氯甲 烷及氯仿。較佳使用四氫呋喃及二氣甲烷。為了進行該反 應，最好先使用呈溶液奉懸浮液型式之甲醆銅（1)，且添加 η莫耳當量之該配位基或此等配位基溶液，並攪拌❶然 後，例如，藉由晶化作用及視需要藉由，例如，碎減壓下 蒸發以移除溶劑或移除部份溶劑後，藉由晶化反應得到甲 酉义銅（I)複合物。藉由此種方法製成^之複合物通常不含甲酸 (χ=〇)，但是，若必要，可以於合成期間添加對應量之甲 酸0 ,
就本發明而言，亦已發現一種製備該新顆f酸銅⑴複合 物之方法，其中該並不报安定之無配位基甲酸銅⑴必需不 能以物質型式經離析及處理。在本方法中，可視需要在惰 性溶劑中使無水甲酸銅（„)與金屬銅（通常以例如，金_屬 線、分散液、顆粒或箱型式之化學比過量使用）及一莫耳 當置甲酸反應。所有惰性溶劑皆適於作為該惰性溶劑，特 別為非質子性極性溶劑。適合之溶劑實料㈣貞，例如， 二乙驗 丙喊、—丁 .驗、四氫°夫喃 第三-丁基甲基醚 或第三-丁基乙基醚； 二氯甲烷及氣仿；及 _化（特別為氧化）烷烴溶劑’例如， 乙腈。較佳使用乙腈。使反應混合物 直到反凰完成為止，其情況通常為經至少 應時間後’較佳至少2小時，更特佳至少4小時，且通等 超過4M、_，較佳不超過36小時，更特佳不超過30小㈣ 其後，以所要化學計量添加所要配也基l，並進一步使 97705.doc 14 ;7〇 應混合物反應，直到複合物形成結束為止。通常，經至少 5分鐘（較佳至少！ 〇分鐘、更牿 . ‘ .30分鐘，且通常不超 ^小時、較佳不超過4小時、更特佳不超❸小時)反應時 二夕複合物之形成完成。接著分離出固體(實質上未 應之銅），移除溶劑，因此得到該產物。在此種製備 新穎甲酸銅⑴複合物之枝中，㈣成複合物含有甲酸， 其含量係根據所選用配位基L及其n數量來確定。 而且，可藉由使這些函化物複合物與甲酸及驗反應以製 備一些該新穎甲酸銅（1)複合物LnC(Hc〇〇)，亦即，此等其 中鹵化物類似物（特別為氣化物類似物LnCuX，其中X為鹵 根/例如，α)係&知。據此，τ以在溶劑中添加所要化 學計量之曱酸至該齒化物複合物内。該曱酸之化學計量至 少與.該画化物複合物之用量一樣多。若欲製備含甲酸(亦 即’其中χ>0)之新穎甲酸銅⑴複合物，則必需適當地選擇 甲酸之化學計量。適合之惰性溶劑特別為所有此等惰性溶 劑，其中副產物自鹼形成，且鹵化物比甲酸銅⑴複合物之 可溶性更佳，或反之亦然。為非質子性極性溶劑特別適 合。適合之溶劑實例為醚類，例如，二乙醚、二丙祕、二 丁醚、四氫呋喃、第三_ 丁基甲基醚或第三_ 丁基乙基醚； 及_化（特別為氣化）院烴溶劑’例如，二氯甲院及氯仿。 較佳使用醚’特別為第三-丁基甲基醚。於這些情況下， 通ΐ ’該甲酸銅（I)複合物之溶解性優於副產物。通常，經 至少5分鐘（較佳至少1〇分鐘、更特佳至少3〇分鐘，且通常 不超過6小時、較佳不超過4小時、更特佳不超過2小時）反 97705.doc -15- 70 應時間後，可完成以甲酸鹽交換該函化物之步驟。接著藉 由添加鹼以沉澱鹵化物。特別適合之鹼為第一、第二或^ -三胺，例如，較佳為三乙胺》進一步於添加鹼後，使該反 應混合物反應，其反應時間通常為至少一小時、較佳至少 2小蛉、更特佳至少4小時，且通常不超過12小時、較佳不 超過8小打、更特佳不超過6小時。然後分離產物及副產 物。在溶劑t若產物比副產物之溶解性更佳，則濾出後 者，接著移除該溶劑。可以在萃取劑内萃取該乾燥殘留物 以進一步純化，接著再自該固體去除萃取劑。適合之萃取 劑為所有溶劑，其中該新穎甲酸銅⑴複合物具可溶性，但 疋该函化氫與鹼之反應產物則不具可溶性，該反應產物係 呈《彳產物型式形成。非質子非極性或微極性溶劑特別適 合。適合之溶劑實例為烷烴或芳香烴，例如，戊烧、己 、元/气油石油、笨或甲苯。較佳使用己烧。於移除此等 固體後才移除萃取劑，因此得到該產物。另一方面，在所 選用溶劑中，若該產物之可溶性比副產物更差，則必需將 其濾出’且若必要’於蒸發溶劑後濾出。 同樣’亦可藉由鹵化銅特別為氯化銅（1))與甲酸及鹼 之反應以得到無配位基曱酸鋼（I)。 於這些反應期間之反應溫度及於溶劑移除期間所使用之 溫度應該夠高，因此可以以令人滿意的速率進行溶劑移除 之反應’但是並不致於高到可以使該甲酸銅⑴開始分解。 通常，已確定溫度為至少_2〇。(：、較佳至少〇°c、更特佳至 少10°C ’且通常不超過8〇r、較佳不超過60〇c、更特佳不 97705.doc 超過40〇C。通常，可 疳 使用至溫（亦即，在20至25t之溫 , 、碭’而且，若必要，可以於減壓下 進行溶劑移除以得到令人滿意的速率。 在所有情況中，較係於起咖a 發人、， 仏於無二氟（特別為氧）之情況下進行 政匕寻&成法。可倍用羽4 羽 α心性氣體方法。適合之惰性氣體 為b知惰性氣體，特別Λ氣 pi 行礼為虱或虱。亦較隹儘可能在無水環 境中操作。 :藉由已知方法（例如，咖、aacvd)或旋塗法塗敷該 新顆甲酸銅⑴複合物至.基片上，並藉以經熱分解或其後進 仃銅^積。可形成凝聚性鋼薄膜。在Μ⑽及旋塗法 人車乂佳在U /合劑中使用呈溶劑型式之新顆甲酸嗣⑴複 口物適合冬惰性溶劑為所有溶劑，其中所使用新穎甲酸 銅⑴複合物具充份.可溶性，且於所使用條件下，對於基/ :不起反應：。其應該亦很容易蒸發，因此很容易移除。適 今之溶劑實例為極性或非極性非質子性溶劑，例如，喊 類’例如’二乙醚、二丙醚、二丁醚、四氫呋喃、第三· 丁基甲基醚或第二· 丁基乙基醚；及鹵化(特別為氯化)烷烴 溶劑’例如’二氯f院及氯仿；烧烴及芳香烴，例如，戊 烧、已烧、汽油、石油 '苯或曱苯。該溶液中之甲酸鹽複 合物濃度之選用可致使該溶液之黏度容易經處理，且=以 形成均勻銅薄膜。通常，使用含至少〇 5(較佳至少3、更特 佳至少5，且通常不超過40、較佳不超過3〇、更特佳不超 過20)重量％該甲酸銅（I)複合物之溶液。 就藉由AACVD塗敷而言，通常將該複合物或複合物溶 97705.doc -17- 1374870 液噴;麗至已加熱基片上，或將該經噴灌基片加熱至分解溫 度。就藉由旋塗法塗敷而言，通常塗敷該複合物或複合物 溶液至旋轉基片上以藉由離心力製成該液體之均勻層。於 塗敷期間或其後將該基片加熱至分解溫度。 就藉由新穎曱酸銅⑴複合物之分解以將銅層沉積在基片 之方法而5，必需於塗敷該複合物期間或其後立即將基片 加熱至該複合物分解溫度以上之溫度。通常，加熱至至少 80°C溫度、較佳至少1〇(rc、更特佳至少i〇5t，且通常不 超過300°C、較佳不超過2S(rc、更特佳不超過25〇<t。 實例 實例1 :甲酸銅⑴之製法 於至溫在氮氣下以5分鐘攪拌添加ο.%克甲酸（2〇毫莫耳） 之20毫升二氣曱烷溶液至丨98克氣化銅（l)CuCi(2〇毫莫耳） 之40毫升無水二氣甲烷懸浮液中。經1〇分鐘後，添加2 克無水三乙胺（20毫莫耳）。再攪拌該混合物，費時4小時， 其中，在逆相玻料上濾出所形成甲酸銅⑴之淺綠色沉澱 物，並經20毫升二氣甲烷洗滌。其產率為％莫耳〇/^ 貫例2 .自甲酸銅（I)及配位基製備新穎複合物之方法 於氮氣下緩慢添加η當量配位基（每8 3毫莫耳一當量）之 20毫升無水二氯甲烷或四氫呋喃溶液至8·3毫莫耳甲酸銅 (I)之20毫升二氯曱烷或THF之攪拌懸浮液内。於各情況下 經約一小時後，甲酸銅⑴已完全溶解。於減壓下已汽提溶 劑後’得到呈無色油或固體之曱酸銅⑴複合物。 實例3 :自氣化銅（I)複合物製備新穎複合物之方法 97705.doc 1374870 於η：下授拌添加，6克(CM莫耳)甲酸至〇1莫耳式LnCua 氣化銅⑴之200毫升甲基第三-丁基喊溶液内，並再持續授 拌-小時。其後，添加1(M克((M莫耳)無水三乙胺，並於 室溫下搜拌5小時。其後，於在減壓下移除溶劑，並 以100毫升己炫萃取g]體殘留物兩次。於4代在減壓下去 除該化合萃取物之己烷，因此得到該產物。 實例4 : π需要離析所形成呈中間物之甲酸銅⑴而製備新 穎複合物之方法 於氮氣下在60毫升無水乙腈中攪拌丨53克無水甲酸銅 (II)Cu(HCOO)2(l〇毫莫耳）、i 6克98%強度之甲酸及2刀克 銅羯’費時24小時。形成含未轉化固體銅之上述無色溶 液。接著一滴滴添加6.65克三乙氧基磷烷（4〇毫莫耳）。再 攪拌反應混合物’費時一小時，然後濾出銅箔。藉由蒸發 遽液得到呈無色液體之產物[(H3CH2CO)3P]2Cu(HCOO) . X HCOOH。 藉由這些方法製成作為實例之曱酸銅（I)複合物 LnCU(HCOO) : X HCOOH及在3丨P-NMR中之膦配位基之化 學位移δ與在13C-NMR及1 H-NMR中之曱酸鹽碳及甲酸鹽質 子之化學位移δ列示在下表中。 97705.doc •19· 1374870
表 配位體L n 根據以下 實例製成 聚集 狀態 31p-nmr δ [ppm] 13C-NMR δ [ppm] 'H-NMR δ [ppm] (H3C)3P 2 2,3 液體 -45.7 166.7 8.4 (H3CH2C)3P 2 2,3 液體 -12.2 165.4 8.3 3 2,3 液體 -14.4 164.3 8.5 [(H3C)2HC]3P 2 2,3 液體 22.1 167.2 8.3 (H3CH2CH2CH2C)3P 2 2,3 液體 -25 165.7 8.4 3 2,3 固體 -22 166.8 8.5 [(H3C)2HCH2C]3P 2 2,3 液體 -28.5 164.1 8.2 (C5H9)3P 2 2,3 固體 8.3 164.7 8.2 3 2,3 固體 9.6 165.2 8.3 (H3CO)3P 2 2,3 液體 126.5 167.3 8.6 3 2,3 液體 -126.9 167 8.6 (H3CH2CO)3P 2 2,3,4 液體 122.9 166.6 8.4 3 2,3 固體 117.9 165.8 8.5 [(H3C)2HCO]3P 2 2,3 固體 117 169 8.2 3 2,3 固體 121.6 168.5 8.3 (F3CH2CO)3P 2 2,3 液體 119.8 159.5 8.1 (C6H5)3P 2 2,3 固體 -3.3 169.2 8.5 (H3C)2HC-NC 2 2 固體 - 140.5 8.2 h3ch2ch2ch2c-nc 2 2 固體 140.5 8.2 (H3C)3C-NC 2 2 固體 - 129 8.5 HnC6-NC 2 2 液體 - 152.4 8.6 97705.doc -20- 1374870 實例 5 : [(H3CH2CO)3P]2Cu(HCOO)之測重研究 如已計算’該複合物[(H3CH2CO)3P]2Cu(HCOO)之熱重 研究確認其由14.4重量％銅及85.6重量％有機組份組成，且 顯示一旦加熱至至少15(TC溫度時，正好損失85 6%其原有 重置。此註明於這些條件下，該複合物可分解成銅及其它 完全不同的氣態分解產物。 實例6 :銅薄膜之沉積 將10%強度之[(H3CH2CO)3P]2Cu(HCOO)之二氣甲烷溶液 喷灑入已加熱至200。(：之燒瓶内。在燒瓶内側上形成銅薄 膜。 實例7 :銅薄膜之沉積 使玻璃燒觀之内表面經10%強度之[(H3CH2C〇)3p]2 Cu(HCOO)之二氣曱烷溶液沾濕。藉由謹慎蒸發溶劑，在 燒瓶之内表面上產生該甲酸鹽複合物之薄膜。然後使燒瓶 加熱至200°C。在燒瓶内側上形成銅薄膜。 97705.doc 21
Claims (1)
1374870
肀請專利範圍: 第093138009號專利申請案 中文申請專利範圍替換本(100年u月） 一種式LnCu(HCOO) . X HCOOH甲酸銅⑴複合物，其中X 為自0至10, η為1、2、3或4’且η個配位基L互相獨立為 各下述配位基： -式WWp磷烷； -式（1^〇)(112〇)(1^0#亞磷酸鹽； -式 R’-NC胩； -式 Rif^CsCI^R4烯烴；或 -式R^CsCR2炔烴； 其中R、R2、R3及R4互相獨立為氫，具有一或2〇個碳原 子之直鏈或分支鏈之視需要經部份或完全氟化之烷基、 胺烷基、烷氧烷基、羥烷基、膦烷基或芳基， 其排除曱酸三苯基膦基銅⑴及甲酸三（二苯基膦基 曱基）乙烷銅（I)。 2. 如請求項1之甲酸銅（I)複合物，其中11為2或3。 3. 如請求項1或2之甲酸銅（I)複合物，其中l係選自以下所 組成之群組：三甲基膦、三乙基膦、三異丙基膦、三_ 正-丁基膦、三異丁基膦、三環戊基膦、三甲氧基膦、三 乙氧基膦、三異丙氧基膦、三（2,2,2-三氟乙氧基）膦、異 丙基胩、正-丁基胩、第三-丁基胩及環己基胩。 4. 如請求項3之曱酸銅（1)複合物，其中l為三_正_ 丁基膦。 5. 如請求項4之曱酸銅⑴複合物，其中乂為1。 種製備如％求項1至5中任一項之曱酸銅（I)複合物之方 法’其係藉由曱酸銅⑴與配位基L在乾惰性溶劑中反 97705-100H25.doc 應。 /年替換頁j 7.如清求項6之方&，其中在反應過程中加入甲酸。 8·如請求項7之方法，其中該甲酸銅（I)係在第一步驟中自 甲酸銅（II)、金屬銅及甲酸得到，且在添加配位基L前並 未經離析。 9. ^種製備如請求項丨至5中任一項之甲酸銅⑴複合物之方 法八係藉由使式LnCu(I)X之鹵化銅⑴複合物與甲酸然 後驗反應，其中 X為齒根’ η為1、2、3或4，且n個配位基L互相獨立為各 下述配位基： -式WWp磷烷； -式（r1〇)(R2〇)(R3o)p亞磷酸鹽； -式R'-NC胩； -式R^R^CsCW烯烴；或 -式 I^C^CR2 炔烴，;） 其中R、R2、R3及R4互相獨立為氫，具有一或2〇個碳原 子之直鍵或分支鏈之視需要經部份或完全氟化之烷 基、胺烷基、烷氧烷基、羥烷基、膦烷基或芳基。 10. —種將金屬銅沉積在基片上之方法，其係塗敷如請求項 1至5中任一項之甲酸鋼⑴複合物至基片上，及於至少8〇t： 之溫度下熱分解該甲酸銅（I)複合物。 11. 如請求項10之方法，其中該曱酸銅⑴複合物係自該氣相 内沉積，並同時分解。 12. 如請求項1〇之方法，其中係以該甲酸銅（1)複合物之溶液 97705-1001125.doc 1374870 〔碎u月‘修正替渙頁丨 喷灑基片，並同時或隨後分解該甲酸酮（I)複合物。 13.如請求項10之方法，其中係塗敷該曱酸銅（I)複合物溶液 至旋轉基片上，並同時或隨後分解該甲酸銅（I)複合物。 97705-1001125.doc
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| AR064292A1 (es) * | 2006-12-12 | 2009-03-25 | Commw Scient Ind Res Org | Dispositivo mejorado para almacenamiento de energia |
| JP5145052B2 (ja) * | 2008-01-07 | 2013-02-13 | 東京エレクトロン株式会社 | 成膜方法および成膜装置、ならびに記憶媒体 |
| DE102010004181A1 (de) | 2009-01-10 | 2011-05-12 | Oliver Feddersen-Clausen | Metallcarboxylatkomplexe mit Alkinligand als verdampfbarer Precursor zur Metall- oder Metalloxidabscheidung |
| US8309179B2 (en) * | 2009-09-28 | 2012-11-13 | Rohm And Haas Electronics Materials Llc | Selenium/group 1b ink and methods of making and using same |
| KR101376913B1 (ko) | 2011-12-27 | 2014-03-20 | 삼성전기주식회사 | 구리 유기금속, 구리 유기금속 제조방법 및 구리 페이스트 |
| KR102564637B1 (ko) * | 2015-07-14 | 2023-08-08 | 고쿠리쓰다이가쿠호진 규슈다이가쿠 | 하이드로실릴화 반응 촉매 |
| CN105435844A (zh) * | 2015-12-22 | 2016-03-30 | 聊城大学 | 一种甲酸铜催化剂及其制备方法与应用 |
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| DE3922233A1 (de) | 1989-07-06 | 1991-01-17 | Guenter Link | Verfahren zur abscheidung von metallen aus metallorganischen verbindungen mittels photonenstrahlung |
| US5141602A (en) * | 1991-06-18 | 1992-08-25 | International Business Machines Corporation | High-productivity method and apparatus for making customized interconnections |
| DE4138722C2 (de) | 1991-11-21 | 1994-05-26 | Dresden Ev Inst Festkoerper | Verfahren zum Verdampfen eines Stoffes für einen sich anschließenden Verarbeitungsprozeß |
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| CN1103257C (zh) | 1998-07-08 | 2003-03-19 | 中国科学技术大学 | 一种以金属配合物热分解制备超细微粉的方法 |
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| JP2003507888A (ja) | 1999-08-18 | 2003-02-25 | ステアーグ アール ティ ピー システムズ インコーポレイテッド | 半導体ウェーハ上に銅の特徴を生じさせる方法 |
| US6369256B1 (en) | 2000-06-09 | 2002-04-09 | National Research Council Of Canada | Self-reducible copper(II) source reagents for chemical vapor deposition of copper metal |
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| EP1697296A2 (de) | 2006-09-06 |
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| US7777059B2 (en) | 2010-08-17 |
| EP1697296B1 (de) | 2014-03-19 |
| JP4463279B2 (ja) | 2010-05-19 |
| CN1894192B (zh) | 2010-05-26 |
| JP2007514687A (ja) | 2007-06-07 |
| KR101253781B1 (ko) | 2013-04-12 |
| DE10360046A1 (de) | 2005-07-21 |
| CN1894192A (zh) | 2007-01-10 |
| KR20060103538A (ko) | 2006-10-02 |
| TW200530153A (en) | 2005-09-16 |
| WO2005058789A2 (de) | 2005-06-30 |
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