JP2004175755A - COPPER COMPLEX HAVING ASYMMETRIC beta-DIKETONE LIGAND AND METHOD FOR PRODUCING THE SAME - Google Patents
COPPER COMPLEX HAVING ASYMMETRIC beta-DIKETONE LIGAND AND METHOD FOR PRODUCING THE SAME Download PDFInfo
- Publication number
- JP2004175755A JP2004175755A JP2002346224A JP2002346224A JP2004175755A JP 2004175755 A JP2004175755 A JP 2004175755A JP 2002346224 A JP2002346224 A JP 2002346224A JP 2002346224 A JP2002346224 A JP 2002346224A JP 2004175755 A JP2004175755 A JP 2004175755A
- Authority
- JP
- Japan
- Prior art keywords
- copper
- group
- diketone
- copper complex
- general formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 150000004699 copper complex Chemical class 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 239000003446 ligand Substances 0.000 title description 4
- 239000010949 copper Substances 0.000 claims abstract description 26
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052802 copper Inorganic materials 0.000 claims abstract description 12
- 150000001336 alkenes Chemical class 0.000 claims abstract description 11
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims abstract description 8
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229940112669 cuprous oxide Drugs 0.000 claims abstract description 8
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 12
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- 125000002729 alkyl fluoride group Chemical group 0.000 claims 1
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 125000005594 diketone group Chemical group 0.000 claims 1
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 239000010409 thin film Substances 0.000 abstract description 4
- 238000005229 chemical vapour deposition Methods 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 150000004696 coordination complex Chemical class 0.000 abstract 1
- 238000000151 deposition Methods 0.000 abstract 1
- 230000008021 deposition Effects 0.000 abstract 1
- 230000008020 evaporation Effects 0.000 abstract 1
- 238000001704 evaporation Methods 0.000 abstract 1
- -1 perfluorocyclopropyl group Chemical group 0.000 description 19
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 238000005160 1H NMR spectroscopy Methods 0.000 description 10
- 150000002430 hydrocarbons Chemical group 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 239000005749 Copper compound Substances 0.000 description 9
- 150000001880 copper compounds Chemical class 0.000 description 9
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 8
- BVPKYBMUQDZTJH-UHFFFAOYSA-N 1,1,1-trifluoro-5,5-dimethylhexane-2,4-dione Chemical compound CC(C)(C)C(=O)CC(=O)C(F)(F)F BVPKYBMUQDZTJH-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 description 7
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 7
- NLXLPOBMBOZAIG-UHFFFAOYSA-N copper(1+);ethenyl(trimethyl)silane Chemical compound [Cu+].C[Si](C)(C)C=C NLXLPOBMBOZAIG-UHFFFAOYSA-N 0.000 description 7
- GCSJLQSCSDMKTP-UHFFFAOYSA-N ethenyl(trimethyl)silane Chemical compound C[Si](C)(C)C=C GCSJLQSCSDMKTP-UHFFFAOYSA-N 0.000 description 7
- 239000011737 fluorine Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000002808 molecular sieve Substances 0.000 description 6
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 5
- 238000000921 elemental analysis Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 229910004028 SiCU Inorganic materials 0.000 description 4
- 239000012024 dehydrating agents Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 150000001342 alkaline earth metals Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229930195734 saturated hydrocarbon Natural products 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 3
- 238000009834 vaporization Methods 0.000 description 3
- 230000008016 vaporization Effects 0.000 description 3
- SHXHPUAKLCCLDV-UHFFFAOYSA-N 1,1,1-trifluoropentane-2,4-dione Chemical compound CC(=O)CC(=O)C(F)(F)F SHXHPUAKLCCLDV-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- MWVFCEVNXHTDNF-UHFFFAOYSA-N hexane-2,3-dione Chemical compound CCCC(=O)C(C)=O MWVFCEVNXHTDNF-UHFFFAOYSA-N 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 1
- CSDQQAQKBAQLLE-UHFFFAOYSA-N 4-(4-chlorophenyl)-4,5,6,7-tetrahydrothieno[3,2-c]pyridine Chemical compound C1=CC(Cl)=CC=C1C1C(C=CS2)=C2CCN1 CSDQQAQKBAQLLE-UHFFFAOYSA-N 0.000 description 1
- XWZIOMULOIOAOA-UHFFFAOYSA-N C(=C)[SiH3].[Cu+] Chemical compound C(=C)[SiH3].[Cu+] XWZIOMULOIOAOA-UHFFFAOYSA-N 0.000 description 1
- 0 CC(C)*(CCC**N)C=C Chemical compound CC(C)*(CCC**N)C=C 0.000 description 1
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 1
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910000102 alkali metal hydride Inorganic materials 0.000 description 1
- 150000008046 alkali metal hydrides Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 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
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 description 1
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- 125000001047 cyclobutenyl group Chemical group C1(=CCC1)* 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
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000004216 fluoromethyl group Chemical group [H]C([H])(F)* 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- QAMFBRUWYYMMGJ-UHFFFAOYSA-N hexafluoroacetylacetone Chemical compound FC(F)(F)C(=O)CC(=O)C(F)(F)F QAMFBRUWYYMMGJ-UHFFFAOYSA-N 0.000 description 1
- QWTDNUCVQCZILF-UHFFFAOYSA-N iso-pentane Natural products CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 1
- 125000005003 perfluorobutyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 1
- 125000005459 perfluorocyclohexyl group Chemical group 0.000 description 1
- 125000005004 perfluoroethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 125000005804 perfluoroheptyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 1
- 125000005005 perfluorohexyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 1
- 125000005008 perfluoropentyl group Chemical group FC(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)* 0.000 description 1
- 125000005009 perfluoropropyl group Chemical group FC(C(C(F)(F)F)(F)F)(F)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 description 1
- 229910000105 potassium hydride Inorganic materials 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical group FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- 125000005425 toluyl group Chemical group 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、銅薄膜層の形成に好適な銅錯体及びその製造方法に関するものである。殊に高速高集積回路配線、すなわち、高速演算回路用の銅配線を化学蒸着法により形成させる際に用いるに好適な銅錯体及びその製造方法に関するものである。
【０００２】
【従来の技術】
電子産業の集積回路分野の製造技術において、高集積化かつ高速化の要求が高まっている。現在、集積回路の大部分にアルミニウム配線が使用されているが、高集積化及び高速化の要求にともなって、より電気抵抗が低く、マイグレーション耐性のある銅による配線技術が実用化されつつある。
【０００３】
銅配線の形成技術については、０価のＣｕスパッタリング法と二価Ｃｕの溶液メッキ法を組み合わせた方法と主に一価Ｃｕの有機金属錯体を用いた化学蒸着法（以下ＭＯＣＶＤ法と記載）とがある。しかしながら、前者のスパッタ法とメッキ法を組み合わせた方法では、０．０７μｍ以下程度の小さい口径を有する深い溝に対する埋め込みが困難である。これを解決する為にＭＯＣＶＤ法が用いられ、高い深さ／口径比（高アスペクト比）の溝や孔及び段差を凹凸が小さく平滑かつ良好な膜質で被覆することが可能となった。
【０００４】
上記のＭＯＣＶＤ用銅化合物としては既に種々のものが知られている。例えば、特許文献１では、１，１，１，５，５，５−ヘキサフルオロアセチルアセトナト銅（Ｉ）ビニルトリメチルシランを用いることを提案している。本銅化合物は、液状である為、供給量を液体流量計で制御でき、蒸気圧も比較的高く、従来の固体の化合物に比し、ＭＯＣＶＤ材料としては、使い易くなっている。
【０００５】
しかしながら、ヘキサフルオロアセチルアセトナート銅（Ｉ）ビニルトリメチルシランは、気化のための長時間加熱によって徐々に分解し、Ｃｕ（Ｏ）の析出があったり、トリメチルビニルシランのオリゴマー及びポリマーが生成し、装置内の閉塞原因となる場合があった。更にヘキサフルオロアセチルアセトナート銅（Ｉ）ビニルトリメチルシランは、弗素含有量が高いことから、これを用いＭＯＣＶＤにより、ＬＳＩ用銅配線を形成した場合、銅配線組成中に弗素が残存し、ＴａＮ，ＴｉＮ等のバリアメタルに対する密着性が、スパッタリング法によるものに比し、極めて劣ることが問題となっている。より、弗素含有量の低い銅化合物が求められている。
【０００６】
この問題点を解決する為に本発明者らは、既に、特許文献２及び特許文献３に示される銅化合物を提案している。しかしながら、これら特許文献で提案した銅化合物の蒸気圧は、高成膜速度を実現する為には、不十分であった。より高い蒸気圧を有する安定な銅化合物が求めらている。
【０００７】
すなわち、市場からは、常に高性能な銅化合物に対する要求があり、特に弗素含有量が低く、高蒸気圧特性を有し、気化温度範囲内で安定であり、２００℃程度の比較的低い温度で分解して、蒸着可能な銅錯体が切望されている。
【０００８】
【特許文献１】
特許第２１３２６９３号
【特許文献２】
特開２００２−１９３９７４号公報
【特許文献３】
特開２００２−１９３９８８号公報
【０００９】
【発明が解決しようとする課題】
本発明は上記の課題に鑑みてなされたものであり、その目的は、従来技術の問題を解決すること、すなわち、本発明は、蒸気圧が高く、気化が安定的かつ容易で、その銅薄膜の形成速度が制御可能な低弗素含有量のＭＯＣＶＤ用銅錯体の提供することにある。
【００１０】
【課題を解決するための手段】
本発明者らは、非対称βジケトン配位子と特定構造のシリル基置換オレフィン配位子との組み合わせを有する銅化合物が熱的に安定であり、蒸気圧が高く、ＭＯＣＶＤ材料として良質の銅薄膜を制御可能な速度で形成可能な銅化合物を見出し、本発明を完成させるに至った。
【００１１】
すなわち、本発明は、下記一般式（１）
【００１２】
【化４】
で示される銅錯体及びその製造方法を提供することにあり、殊に上記一般式（１）で示される銅錯体は、Ｃｕ−ＭＯＣＶＤ材料として銅薄膜形成に有用である。
【００１３】
以下、本発明の詳細について説明する。
【００１４】
上記一般式（１）おいてＲ１，Ｒ２は、炭素数１乃至２０、好ましくは、銅錯体の蒸気圧を上昇させるために炭素数１乃至１０の炭化水素基であり、Ｒ１どうし、Ｒ２どうしは、同一であっても異なっても良い。
【００１５】
炭化水素基としては、特に限定されるものではないが、炭素数１〜２０、好ましくは炭素数１〜１０のアルキル基、アリール基、アリールアルキル基、アルキルアリール基を挙げることができる。
【００１６】
具体的には、例えば、メチル、エチル、ｎ−プロピル、ｉ−プロピル、ｎ−ブチル、ｉ−ブチル、ｓｅｃ−ブチル、ｔｅｒｔ．−ブチル、ｎ−ペンチル、ｔｅｒｔ．−アミル、ｎ−ヘキシル、シクロヘキシル、フェニル、トルイル基等をあげることができる。
【００１７】
Ｒｆは、少なくとも一つの弗素原子を有する炭素数１〜２０の弗化炭化水素基である。弗化炭化水素基としては、少なくとも一つの弗素原子を有する炭化水素基であれば特に限定されるものではなく、炭素数１〜２０、好ましくは炭素数１〜１０の弗化飽和炭化水素基や弗化不飽和炭化水素基等をあげることができる。
【００１８】
弗化飽和炭化水素基としては、例えば、トリフルオロメチル基、パーフルオロエチル基、パーフルオロプロピル基、パーフルオロシクロプロピル基、パーフルオロメチルシクロプロピル基、パーフルオロブチル基、パーフルオロシクロブチル基、パーフルオロペンチル基、パーフルオロシクロペンチル基、パーフルオロメチルシクロペンチル基、パーフルオロヘキシル基、パーフルオロシクロヘキシル基、パーフルオロ−１，２−ジメチルシクロヘキシル基、パーフルオロヘプチル基等のパーフルオロカーボン残基、フルオロメチル基、ジフルオロメチル基、１，１，１−トリフルオロエチル基、２−パーフルオロアルキルエチル基のフルオロハイドロカーボン残基等を挙げることができる。
【００１９】
更に弗化不飽和炭化水素基としては、例えば、パーフルオロエテニル基、パーフルオロプロペニル基、パーフルオロ−１，３−ブタジエニル基、シクロブテニル基、パーフルオロ−２−ブチニル基、ペンタフルオロフェニル基、パーフルオロトルイル基、ビス（トリフルオロメチル）フェニル基、パーフルオロナフタレニル基、パーフルオロインデニル基、パーフルオロフルオレニル基等を挙げることができる。
【００２０】
ｎは、０乃至２０の整数、好ましくは０乃至１０の整数、特に好ましくは０乃至２の整数を表す。
【００２１】
続いて、上記一般式（１）の非対称βジケトン配位銅錯体の製造の際に用いることができる原料について説明する。
【００２２】
銅（Ｉ）原料としては、特に限定されるものではないが、塩化銅（Ｉ）、臭化銅（Ｉ）、沃化銅（Ｉ）等のハロゲン化銅（Ｉ）化合物や酸化第一銅を用いることができる。
【００２３】
シリル基置換アルケンとしては、下記一般式（２）のシリル基置換アルケンを用いることができる。
【００２４】
【化５】
βジケトン成分としては、下記一般式（３）のβジケトン又は下記一般式（４）のβジケトン塩を用いることができる。
【００２５】
【化６】
【００２６】
【化７】
一般式（１）の非対称βジケトン配位銅錯体の製造方法については、特に限定されるものではないが、一般式（２）のシリル基置換アルケンの共存下、一般式（３）のβジケトンに酸化第一銅を反応させることによって製造することができる。
【００２７】
この際の量論比については、特に限定されないが、β−ジケトン１ｍｏｌに対し、酸化第一銅が０．０１ｍｏｌ乃至１００ｍｏｌ、好ましくは、０．５ｍｏｌ乃至５０ｍｏｌ、特に好ましくは、０．１ｍｏｌ乃至１０ｍｏｌの範囲であり、シリル基置換アルケンが０．０１ｍｏｌ乃至５００ｍｏｌ、好ましくは、０．５ｍｏｌ乃至２５０ｍｏｌ、特に好ましくは、０．１ｍｏｌ乃至５０ｍｏｌの範囲で添加することができる。この範囲を外れた場合、目的物である非対称βジケトン配位銅錯体の収量が低くなったり、精製が困難となる場合がある。
【００２８】
一般式（２）のシリル基置換アルケンの共存下、一般式（３）のβジケトンに酸化第一銅を反応させる場合、副生する水をモレキュラーシーブ、硫酸マグネシウム、硫酸ナトリウム、炭酸ナトリウム等の脱水剤を共存させて除去することが好ましい。脱水剤を共存させることにより、目的物の非対称βジケトン配位銅錯体の収率が向上する場合がある。
【００２９】
また、一般式（１）の非対称βジケトン配位銅錯体は、一般式（２）のシリル基置換アルケン共存下、一般式（４）のβ−ジケトン塩にハロゲン化銅（Ｉ）化合物を反応させることによっても製造することができる。
【００３０】
この際の量論比については、特に限定されないが、βジケトン塩１ｍｏｌに対し、ハロゲン化銅（Ｉ）化合物が０．０１ｍｏｌ乃至１００ｍｏｌ、好ましくは、０．５ｍｏｌ乃至５０ｍｏｌ、特に好ましくは、０．１ｍｏｌ乃至１０ｍｏｌの範囲であり、シリル基置換アルケンが０．０１ｍｏｌ乃至５００ｍｏｌ、好ましくは、０．５ｍｏｌ乃至２５０ｍｏｌ、特に好ましくは、０．１ｍｏｌ乃至５０ｍｏｌの範囲で添加することができる。この範囲を外れた場合、目的物である非対称βジケトン配位銅錯体の収量が低くなったり、精製が困難となる場合がある。
【００３１】
一般式（４）で示されるβジケトン塩の製造方法としては、βジケトンと水素化ナトリウム、水素化カリウム等の水素化アルカリ金属とを反応させるか、又はβジケトンと水素化カルシウム等の水素化アルカリ土類金属とを反応させることにより製造することができる。また、βジケトンと水酸化ナトリウム、水酸化カリウム等の水酸化アルカリ金属とを反応させるか、又はβジケトンと水酸化マグネシウム、水酸化カルシウム等の水酸化アルカリ土類金属とを反応させることによっても製造できる。この際、副生する水をモレキュラーシーブ、硫酸マグネシウム、硫酸ナトリウム、炭酸ナトリウム等の脱水剤を共存させて除去することが望ましい。脱水剤を共存させることにより、目的物の非対称βジケトン配位銅錯体の収率が向上する場合がある。
【００３２】
Ｍであるアルカリ金属及びアルカリ土類金属としては、Ｌｉ、Ｎａ、Ｋ、Ｍｇ、Ｃａ等が挙げられる。
【００３３】
非対称βジケトン配位銅錯体を製造する際、溶媒非存在下、又は溶媒存在下で反応を行うことができる。溶媒の種類は、当該技術分野で使用されるものであれば特に限定されるものではない。例えば、ｎ−ペンタン、ｉ−ペンタン、ｎ−ヘキサン、ｎ−ヘプタン、ｎ−デカン等の飽和炭化水素類、トルエン、キシレン、デセン−１等の不飽和炭化水素類、ジエチルエーテル、テトラヒドロフラン、テトラヒドロピラン等のエーテル類、ジクロロメタン、ジクロロエタン、クロロホルム、クロロベンゼン等のハロゲン化炭化水素類を挙げることができる。
【００３４】
しかしながら、溶媒希釈しない製造法を用いることにより、非対称βジケトン配位銅錯体の顕著な収率向上及び反応器当りの収量向上が観られる場合がある。
【００３５】
銅錯体を製造する際の反応温度については、特に限定されないが、生成する銅錯体が分解しない様な温度範囲で行うことが好ましい。通常、工業的に使用されている温度である−７８〜２００℃の範囲、好ましくは、−５０〜１５０℃の範囲で行うことが好ましい。反応の圧力条件は、加圧下、常圧下、減圧下いずれであっても可能である。
【００３６】
製造された非対称βジケトン配位銅錯体の精製法については特に限定されないが、減圧蒸留及びシリカ、アルミナ、高分子ゲルを用いたカラム分離精製を使用することができる。この際の操作は、当該有機金属化合物合成分野での方法に従えばよい。すなわち、例えば、脱水及び脱酸素された窒素又はアルゴン雰囲気下で行い、使用する溶媒及び精製用のカラム充填剤等は、予め脱水操作を施しておくことが好ましい。この操作により、生成する銅錯体の収量及び純度が向上する場合がある。
【００３７】
以下に実施例を示すが、本発明は、これらの実施例によって何ら限定されるものではない。
【００３８】
【実施例】
実施例１
［非対称βジケトンアルカリ金属塩の製造］
窒素気流下、攪拌装置を有する５００ｍｌのガラス製反応器に、１，１，１−トリフルオロ−５，５−ジメチル−２，４−ヘキサンジオン２８．１ｇ（１４３ｍｍｏｌ）を脱水したテトラヒドロフラン４００ｍｌに希釈し、８５％純度の水酸化カリウム９．４６ｇ（１４３ｍｍｏｌ）及びモレキュラーシーブ２００ｍｌを添加し、室温で４時間攪拌し１，１，１−トリフルオロ−５，５−ジメチル−２，４−ヘキサンジオンのカリウム塩溶液を得た。反応後、モレキュラーシーブをガラスフィルターで除去し、得られた濾液からテトラヒドロフランを減圧留去し、ｎ−ペンタンでスラリー化し、ガラスフィルターで目的物である１，１，１−トリフルオロ−５，５−ジメチル−２，４−ヘキサンジオンのカリウム塩２０．５ｇ（８７．４ｍｍｏｌ）を得た。収率は、６１．０％であった。
［非対称βジケトン配位銅（Ｉ）錯体の製造］
窒素気流下、攪拌装置を有する２００ｍｌのシュレンク管に１，１，１−トリフルオロ−５，５−ジメチル−２，４−ヘキサンジオンのカリウム塩７．０３ｇ（３０．０ｍｍｏｌ）、塩化第一銅３．５６ｇ（３６．０ｍｍｏｌ）、ビニルトリメチルシラン１５．０ｇ（１５０ｍｍｏｌ）を仕込み、これに乾燥ｎ−ペンタン１５０ｍｌを加え、反応を開始した。室温で２７時間反応させた後、未反応物及び副生物である塩化カリウムをガラスフィルターで除去し、得られた濾液からｎ−ペンタンを留去し、目的物である（１，１，１−トリフルオロ−５，５−ジメチル−２，４−ヘキサンジオナト）銅（Ｉ）ビニルトリメチルシランの濃青色液体８．４３ｇ（２３．５ｍｏｌ）を得た。収率は、７８．３％（カリウム塩基準）に相当した。目的物を室温にて保存したがその分解は無く、安定であった。
【００３９】
目的物の元素分析及び１Ｈ−ＮＭＲの結果は以下の通りであった。
Ｃ１３Ｈ２２Ｏ２Ｆ３ＳｉＣｕ （ｗｔ％）
測定値（Ｃ：４３．２，Ｈ：６．２，Ｆ：１６．３，Ｃｕ：１７．４，Ｓｉ：７．９，Ｋ：検出されず）
計算値（Ｃ：４３．５，Ｈ：６．１，Ｆ：１５．９，Ｃｕ：１７．７，Ｓｉ：７．８，Ｋ：０．０）
１Ｈ−ＮＭＲ（ｉｎ Ｃ６Ｄ６） δ０．０９６ｐｐｍ（９Ｈ，ｓ，ＳｉＣＨ３）、δ１．０９ｐｐｍ（９Ｈ，ｓ，ｔＢｕ（Ｃ＝Ｏ））、δ４．１１ｐｐｍ（３Ｈ，ｍ，ＣＨ２ＣＨ−）、δ６．１８ｐｐｍ（１Ｈ，ｓ，（Ｃ＝Ｏ）ＣＨ（Ｃ＝Ｏ））
隔膜式蒸気圧測定装置により、本錯体の蒸気圧測定を行ったところ、５０℃で１９９Ｐａであり、ＭＯＣＶＤ材料として十分な蒸気圧を有していることが判明した。
【００４０】
実施例２
実施例１において、ビニルトリメチルシランに変えて、ビニル−ｔｅｒｔ．−ブチルジメチルシラン２１．３ｇ（１５０ｍｍｏｌ）としたこと以外は、実施例１と同様にして、目的物である（１，１，１−トリフルオロ−５，５−ジメチル−２，４−ヘキサンジオナト）銅（Ｉ）ビニル−ｔｅｒｔ．−ブチルジメチルシランの製造を行った。結果は、目的物の濃青色液体を収率６９．１％で得た。目的物を室温にて保存したがその分解は無く、安定であった。
【００４１】
元素分析及び１Ｈ−ＮＭＲの結果は、以下の通りであった。
Ｃ１６Ｈ２８Ｏ２Ｆ３ＳｉＣｕ （ｗｔ％）
測定値（Ｃ：４７．１，Ｈ：６．８，Ｆ：１４．４，Ｃｕ：１５．７，Ｓｉ：７．１，Ｋ：検出されず）
計算値（Ｃ：４７．９，Ｈ：７．０，Ｆ：１４．２，Ｃｕ：１５．９，Ｓｉ：７．０，Ｋ：０．０）
１Ｈ−ＮＭＲ（ｉｎ Ｃ６Ｄ６） δ０．０９５ｐｐｍ（６Ｈ，ｓ，ＳｉＣＨ３）、δ０．８００ｐｐｍ（９Ｈ，ｓ，ＳｉｔＢｕ）、δ１．０７ｐｐｍ（９Ｈ，ｓ，ｔＢｕ（Ｃ＝Ｏ））、δ４．１０ｐｐｍ（３Ｈ，ｍ，ＣＨ２ＣＨ−）、δ６．１７ｐｐｍ（１Ｈ，ｓ，（Ｃ＝Ｏ）ＣＨ（Ｃ＝Ｏ））
隔膜式蒸気圧測定装置により、本錯体の蒸気圧測定を行ったところ、５０℃で２４．７Ｐａであり、ＭＯＣＶＤ材料として十分な蒸気圧を有していることが判明した。
【００４２】
実施例３
窒素気流下、攪拌装置を有する１００ｍｌのシュレンク管に１，１，１−トリフルオロ−５，５−ジメチル−２，４−ヘキサンジオン５．８９ｇ（３０．０ｍｍｏｌ）、酸化第一銅５．１５ｇ（３６．０ｍｍｏｌ）、ビニルトリメチルシラン１５．０ｇ（１５０ｍｍｏｌ）、モレキュラーシーブ３０ｍｌを仕込み、室温で２２時間攪拌反応させた。モレキュラーシーブ及び未反応の酸化第一銅をガラスフィルターで除去し、濾液から、未反応の１，１，１−トリフルオロ−５，５−ジメチル−２，４−ヘキサンジオン及びビニルトリメチルシランを減圧条件下留去し、目的物である１，１，１−トリフルオロ−５，５−ジメチル−２，４−ヘキサンジオナト）銅（Ｉ）ビニルトリメチルシランの濃青色液体１０．０５ｇ（２８．０ｍｏｌ）を得た。収率は、９３．３％（ヘキサンジオン基準）に相当し、極めて高収率であり、無溶媒での製造の効果が確認された。目的物を室温にて保存したがその分解は無く、安定であった。
【００４３】
目的物の元素分析及び１Ｈ−ＮＭＲの結果は以下の通りであった。
Ｃ１３Ｈ２２Ｏ２Ｆ３ＳｉＣｕ （ｗｔ％）
測定値（Ｃ：４３．２，Ｈ：６．２，Ｆ：１６．３，Ｃｕ：１７．４，Ｓｉ：７．９）
計算値（Ｃ：４３．５，Ｈ：６．１，Ｆ：１５．９，Ｃｕ：１７．７，Ｓｉ：７．８）
１Ｈ−ＮＭＲ（ｉｎ Ｃ６Ｄ６） δ０．０８８ｐｐｍ（９Ｈ，ｓ，ＳｉＣＨ３）、δ１．０８ｐｐｍ（９Ｈ，ｓ，ｔＢｕ（Ｃ＝Ｏ））、δ４．１０ｐｐｍ（３Ｈ，ｍ，ＣＨ２ＣＨ−）、δ６．１６ｐｐｍ（１Ｈ，ｓ，（Ｃ＝Ｏ）ＣＨ（Ｃ＝Ｏ））
比較例１
実施例１において、１，１，１−トリフルオロ−５，５−ジメチル−２，４−ヘキサンジオンに変えて、１，１，１−トリフルオロアセチルアセトン用いたこと以外は、実施例１と同様にして１，１，１−トリフルオロアセチルアセトンのカリウム塩を得、目的物である（１，１，１−トリフルオロアセチルアセトナト）銅（Ｉ）ビニルトリメチルシランの濃青色液体を得た。収率は、５７．３％であった。本濃青色液体の１Ｈ−ＮＭＲは、以下の通りである。
【００４４】
１Ｈ−ＮＭＲ（ｉｎ Ｃ６Ｄ６） δ０．０６８ｐｐｍ（９Ｈ，ｓ，ＳｉＣＨ３）、δ１．７４ｐｐｍ（３Ｈ，ｓ，ＣＨ３（Ｃ＝Ｏ））、δ４．１２ｐｐｍ（３Ｈ，ｂｒｏａｄ，ＣＨ２＝ＣＨ−）、δ５．７３ｐｐｍ（１Ｈ，ｓ，（Ｃ＝Ｏ）ＣＨ（Ｃ＝Ｏ））
しかしながら、本１，１，１−トリフルオロアセチルアセトナト）銅（Ｉ）ビニルトリメチルシランの濃青色液体を窒素雰囲気下、室温にて３時間放置したところ、緑色固体及び黄金色の金属銅が析出し、目的物の液体がすべて固化した。すなわち、室温で本銅錯体が不安定で分解し易く、ＭＯＣＶＤ材料としては不適であることが認められた。
【００４５】
比較例２
実施例１において、ビニルトリメチルシランに変えて、ビニルトリエトキシシラン２８．５ｇ（１５０ｍｍｏｌ）を用いたこと以外は、実施例１と同様にして非対称βジケトン銅（Ｉ）錯体を製造したが、青緑色の固体が得られたのみであった。元素分析を行ったところＣｕ含有量が３．４ｗｔ％であった。計算値の１４．２ｗｔ％とはかけ離れており、目的の錯体が合成されていないことが判明した。
比較例３
実施例１において、１，１，１−トリフルオロ−５，５−ジメチル−２，４−ヘキサンジオンにかえて、１，１，１，５，５，５−ヘキサフルオロアセチルアセトン２９．８ｇ（１４３ｍｍｏｌ）とし、ビニルトリメチルシランにかえて、ビニル−ｔｅｒｔ．−ブチルジメチルシラン２１．３ｇ（１５０ｍｍｏｌ）としたこと以外は、実施例１と同様にして、目的物である（１，１，１，５，５，５−ヘキサフルオロアセチルアセトナト）銅（Ｉ）ビニル−ｔｅｒｔ．−ブチルジメチルシランを製造した。結果は、目的物の濃緑色液体を収率８３．０％で得た。目的物を室温にて保存したが、その分解は無く、安定であった。
【００４６】
元素分析及び１Ｈ−ＮＭＲの結果は、以下の通りであった。
Ｃ１３Ｈ１９Ｏ２Ｆ６ＳｉＣｕ （ｗｔ％）
測定値（Ｃ：３７．４，Ｈ：４．６，Ｆ：２８．０，Ｃｕ：１５．２，Ｓｉ：６．７，Ｋ検出されず）
計算値（Ｃ：３７．８，Ｈ：４．６，Ｆ：２７．６，Ｃｕ：１５．４，Ｓｉ：６．８，Ｋ：０．０）
１Ｈ−ＮＭＲ（ｉｎ Ｃ６Ｄ６） δ０．０９２ｐｐｍ（６Ｈ，ｓ，ＳｉＣＨ３）、δ０．７９ｐｐｍ（９Ｈ，ｓ，Ｓｉ−ｔＢｕ）、δ４．２０ｐｐｍ（３Ｈ，ｍ，ＣＨ２ＣＨ−）、δ６．２１ｐｐｍ（１Ｈ，ｓ，（Ｃ＝Ｏ）ＣＨ（Ｃ＝Ｏ））
隔膜式蒸気圧測定装置により、本錯体の蒸気圧測定を行ったところ、５０℃で２．２Ｐａであり、実施例１乃至３で製造したＣｕ（Ｉ）錯体よりも低い蒸気圧を有していた。
【００４７】
【発明の効果】
本発明によれば、以下の顕著な効果が奏される。
【００４８】
本発明の第一の効果としては、従来の弗素含有βジケトン銅（Ｉ）ビニルシラン錯体よりも弗素含有量が低く、安定であり、蒸気圧が高い新規な銅錯体を提供することが可能となった。殊に本錯体は、銅配線用ＭＯＣＶＤ材料として好適である。
【００４９】
第二の効果としては、非対称β−ジケトンを配位子として有する銅（Ｉ）錯体を製造するにあたり、極めて効率的で、経済的な合成処方を提供することが可能となった。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a copper complex suitable for forming a copper thin film layer and a method for producing the same. In particular, the present invention relates to a copper complex suitable for use in forming a high-speed high-integration circuit wiring, that is, a copper wiring for a high-speed arithmetic circuit by a chemical vapor deposition method, and a method for producing the same.
[0002]
[Prior art]
2. Description of the Related Art In manufacturing technology in the field of integrated circuits in the electronics industry, demands for high integration and high speed are increasing. At present, aluminum wiring is used for most integrated circuits. However, with the demand for higher integration and higher speed, a wiring technique using copper having lower electric resistance and migration resistance is being put to practical use.
[0003]
Regarding the technology for forming copper wiring, there are a method of combining a zero-valent Cu sputtering method and a solution plating method of divalent Cu, and a chemical vapor deposition method (hereinafter, referred to as MOCVD method) mainly using an organometallic complex of monovalent Cu. There is. However, in the former method in which the sputtering method and the plating method are combined, it is difficult to fill a deep groove having a small diameter of about 0.07 μm or less. In order to solve this, the MOCVD method has been used, and it has become possible to coat grooves, holes and steps having a high depth / diameter ratio (high aspect ratio) with small unevenness and smooth and excellent film quality.
[0004]
Various compounds are already known as the copper compound for MOCVD. For example, Patent Document 1 proposes using 1,1,1,5,5,5-hexafluoroacetylacetonato copper (I) vinyltrimethylsilane. Since the present copper compound is liquid, the supply amount can be controlled by a liquid flow meter, the vapor pressure is relatively high, and it is easier to use as a MOCVD material than a conventional solid compound.
[0005]
However, hexafluoroacetylacetonate copper (I) vinyltrimethylsilane is gradually decomposed by prolonged heating for vaporization, Cu (O) is precipitated, and oligomers and polymers of trimethylvinylsilane are generated, and the In some cases could cause obstruction. Further, since hexafluoroacetylacetonate copper (I) vinyltrimethylsilane has a high fluorine content, when MOCVD is used to form copper wiring for LSI, fluorine remains in the copper wiring composition, and TaN, The problem is that the adhesion to a barrier metal such as TiN is extremely inferior to that obtained by a sputtering method. Therefore, a copper compound having a low fluorine content is required.
[0006]
In order to solve this problem, the present inventors have already proposed copper compounds disclosed in Patent Documents 2 and 3. However, the vapor pressure of the copper compound proposed in these patent documents was insufficient for realizing a high film forming rate. There is a need for a stable copper compound having a higher vapor pressure.
[0007]
That is, there is always a demand from the market for a high-performance copper compound, especially a low fluorine content, high vapor pressure characteristics, stable within the vaporization temperature range, and a relatively low temperature of about 200 ° C. There is a long-felt need for a copper complex that can be decomposed and deposited.
[0008]
[Patent Document 1]
Patent No. 2132693 [Patent Document 2]
JP 2002-193974 A [Patent Document 3]
Japanese Patent Application Laid-Open No. 2002-193988
[Problems to be solved by the invention]
The present invention has been made in view of the above problems, and an object of the present invention is to solve the problems of the prior art. That is, the present invention has a high vapor pressure, stable and easy vaporization, and a copper thin film. It is an object of the present invention to provide a copper complex for MOCVD having a low fluorine content and capable of controlling the formation rate of the compound.
[0010]
[Means for Solving the Problems]
The present inventors have found that a copper compound having a combination of an asymmetric β-diketone ligand and a silyl group-substituted olefin ligand having a specific structure is thermally stable, has a high vapor pressure, and has a high quality as a MOCVD material. The present inventors have found a copper compound that can be formed at a rate that can control the concentration of the compound, and have completed the present invention.
[0011]
That is, the present invention provides the following general formula (1)
[0012]
Embedded image
In particular, the copper complex represented by the general formula (1) is useful as a Cu-MOCVD material for forming a copper thin film.
[0013]
Hereinafter, details of the present invention will be described.
[0014]
The general formula (1) Oite R 1, R 2 is 1 to 20 carbon atoms, preferably a hydrocarbon group having 1 to 10 carbon atoms in order to increase the vapor pressure of copper complex, and if R 1, R 2 may be the same or different.
[0015]
Although it does not specifically limit as a hydrocarbon group, C1-C20, Preferably a C1-C10 alkyl group, an aryl group, an arylalkyl group, and an alkylaryl group can be mentioned.
[0016]
Specifically, for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert. -Butyl, n-pentyl, tert. -Amyl, n-hexyl, cyclohexyl, phenyl, toluyl and the like.
[0017]
R f is a C 1-20 fluorinated hydrocarbon group having at least one fluorine atom. The fluorinated hydrocarbon group is not particularly limited as long as it is a hydrocarbon group having at least one fluorine atom, and may be a fluorinated saturated hydrocarbon group having 1 to 20, preferably 1 to 10 carbon atoms. And fluorinated unsaturated hydrocarbon groups.
[0018]
Examples of the fluorinated saturated hydrocarbon group include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorocyclopropyl group, a perfluoromethylcyclopropyl group, a perfluorobutyl group, a perfluorocyclobutyl group, Perfluorocarbon residues such as perfluoropentyl group, perfluorocyclopentyl group, perfluoromethylcyclopentyl group, perfluorohexyl group, perfluorocyclohexyl group, perfluoro-1,2-dimethylcyclohexyl group, perfluoroheptyl group, fluoromethyl Groups, a difluoromethyl group, a 1,1,1-trifluoroethyl group, a fluorohydrocarbon residue of a 2-perfluoroalkylethyl group, and the like.
[0019]
Further, as a fluorinated unsaturated hydrocarbon group, for example, a perfluoroethenyl group, a perfluoropropenyl group, a perfluoro-1,3-butadienyl group, a cyclobutenyl group, a perfluoro-2-butynyl group, a pentafluorophenyl group, Examples include a perfluorotoluyl group, a bis (trifluoromethyl) phenyl group, a perfluoronaphthalenyl group, a perfluoroindenyl group, and a perfluorofluorenyl group.
[0020]
n represents an integer of 0 to 20, preferably an integer of 0 to 10, and particularly preferably an integer of 0 to 2.
[0021]
Next, the raw materials that can be used in the production of the asymmetric β-diketone-coordinated copper complex represented by the general formula (1) will be described.
[0022]
The copper (I) raw material is not particularly limited, but copper (I) compounds such as copper (I) chloride, copper (I) bromide, and copper (I) iodide, and cuprous oxide Can be used.
[0023]
As the silyl group-substituted alkene, a silyl group-substituted alkene represented by the following general formula (2) can be used.
[0024]
Embedded image
As the β-diketone component, a β-diketone represented by the following general formula (3) or a β-diketone salt represented by the following general formula (4) can be used.
[0025]
Embedded image
[0026]
Embedded image
[0027]
The stoichiometric ratio at this time is not particularly limited, but the cuprous oxide is 0.01 mol to 100 mol, preferably 0.5 mol to 50 mol, particularly preferably 0.1 mol to 10 mol, per 1 mol of β-diketone. And the silyl group-substituted alkene can be added in an amount of 0.01 mol to 500 mol, preferably 0.5 mol to 250 mol, particularly preferably 0.1 mol to 50 mol. Outside this range, the yield of the target asymmetric β-diketone-coordinated copper complex may be low, or purification may be difficult.
[0028]
When cuprous oxide is reacted with a β-diketone of the general formula (3) in the presence of a silyl group-substituted alkene of the general formula (2), water produced as a by-product such as molecular sieve, magnesium sulfate, sodium sulfate, and sodium carbonate is used. It is preferable to remove in the presence of a dehydrating agent. The coexistence of a dehydrating agent may improve the yield of the target asymmetric β-diketone-coordinated copper complex.
[0029]
Further, the asymmetric β-diketone-coordinated copper complex of the general formula (1) is obtained by reacting a copper (I) halide compound with a β-diketone salt of the general formula (4) in the presence of a silyl group-substituted alkene of the general formula (2). It can also be manufactured by performing the above.
[0030]
The stoichiometric ratio at this time is not particularly limited, but the amount of the copper (I) halide is 0.01 mol to 100 mol, preferably 0.5 mol to 50 mol, particularly preferably 0.1 mol to 1 mol of the β-diketone salt. It is in the range of 1 mol to 10 mol, and the silyl group-substituted alkene can be added in the range of 0.01 mol to 500 mol, preferably 0.5 mol to 250 mol, particularly preferably 0.1 mol to 50 mol. Outside this range, the yield of the target asymmetric β-diketone-coordinated copper complex may be low, or purification may be difficult.
[0031]
The method for producing the β-diketone salt represented by the general formula (4) includes reacting the β-diketone with an alkali metal hydride such as sodium hydride, potassium hydride, or hydrogenating the β-diketone with calcium hydride or the like. It can be produced by reacting with an alkaline earth metal. Alternatively, by reacting β-diketone with an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, or by reacting β-diketone with an alkaline earth metal hydroxide such as magnesium hydroxide or calcium hydroxide. Can be manufactured. At this time, it is desirable to remove by-product water in the presence of a dehydrating agent such as molecular sieve, magnesium sulfate, sodium sulfate, and sodium carbonate. The coexistence of a dehydrating agent may improve the yield of the target asymmetric β-diketone-coordinated copper complex.
[0032]
Examples of the alkali metal and alkaline earth metal as M include Li, Na, K, Mg, Ca and the like.
[0033]
When producing an asymmetric β-diketone coordinated copper complex, the reaction can be performed in the absence of a solvent or in the presence of a solvent. The type of the solvent is not particularly limited as long as it is used in the art. For example, saturated hydrocarbons such as n-pentane, i-pentane, n-hexane, n-heptane, n-decane, unsaturated hydrocarbons such as toluene, xylene and decene-1, diethyl ether, tetrahydrofuran, tetrahydropyran And halogenated hydrocarbons such as dichloromethane, dichloroethane, chloroform and chlorobenzene.
[0034]
However, by using a production method without solvent dilution, a remarkable improvement in the yield of an asymmetric β-diketone-coordinated copper complex and an improvement in the yield per reactor may be observed.
[0035]
The reaction temperature for producing the copper complex is not particularly limited, but it is preferable to carry out the reaction in a temperature range that does not decompose the produced copper complex. Usually, it is preferably carried out in a temperature range of −78 to 200 ° C., which is industrially used, and preferably in a range of −50 to 150 ° C. The pressure condition of the reaction can be any of under pressure, normal pressure and reduced pressure.
[0036]
The method for purifying the produced asymmetric β-diketone-coordinated copper complex is not particularly limited, but distillation under reduced pressure and column separation and purification using silica, alumina, or a polymer gel can be used. The operation at this time may be in accordance with the method in the field of synthesis of the organometallic compound. That is, for example, it is preferable that the dehydration and deoxygenation be performed in a nitrogen or argon atmosphere, and the solvent to be used and the column packing for purification be dehydrated in advance. This operation may improve the yield and purity of the produced copper complex.
[0037]
Examples are shown below, but the present invention is not limited to these examples.
[0038]
【Example】
Example 1
[Production of alkali metal salt of asymmetric β-diketone]
Under a nitrogen stream, 28.1 g (143 mmol) of 1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedione was diluted with 400 ml of dehydrated tetrahydrofuran in a 500 ml glass reactor having a stirrer. Then, 9.46 g (143 mmol) of potassium hydroxide having a purity of 85% and 200 ml of molecular sieve were added, and the mixture was stirred at room temperature for 4 hours and 1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedione. Was obtained as a potassium salt solution. After the reaction, the molecular sieve was removed with a glass filter, tetrahydrofuran was distilled off from the obtained filtrate under reduced pressure, and the slurry was slurried with n-pentane, and the target 1,1,1-trifluoro-5,5 was filtered with a glass filter. 20.5 g (87.4 mmol) of potassium salt of -dimethyl-2,4-hexanedione were obtained. The yield was 61.0%.
[Production of asymmetric β-diketone-coordinated copper (I) complex]
Under a nitrogen stream, 7.03 g (30.0 mmol) of potassium salt of 1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedione was placed in a 200 ml Schlenk tube having a stirrer, and cuprous chloride. 3.56 g (36.0 mmol) and 15.0 g (150 mmol) of vinyltrimethylsilane were charged, and 150 ml of dry n-pentane was added thereto to start the reaction. After reacting at room temperature for 27 hours, unreacted substances and potassium chloride as a by-product were removed by a glass filter, and n-pentane was distilled off from the obtained filtrate to obtain the desired product (1,1,1- 8.43 g (23.5 mol) of a deep blue liquid of trifluoro-5,5-dimethyl-2,4-hexanedionato) copper (I) vinyltrimethylsilane was obtained. The yield corresponded to 78.3% (based on potassium salt). The target product was stored at room temperature, but did not decompose and was stable.
[0039]
The results of elemental analysis and 1 H-NMR of the target product were as follows.
C 13 H 22 O 2 F 3 SiCu (wt%)
Measurement value (C: 43.2, H: 6.2, F: 16.3, Cu: 17.4, Si: 7.9, K: not detected)
Calculated values (C: 43.5, H: 6.1, F: 15.9, Cu: 17.7, Si: 7.8, K: 0.0)
1 H-NMR (in C 6 D 6 ) δ 0.096 ppm (9H, s, SiCH 3 ), δ 1.09 ppm (9 H, s, t Bu (C = O)), δ 4.11 ppm (3H, m, CH 2) CH—), δ 6.18 ppm (1H, s, (C ＝ O) CH (C ＝ O))
When the vapor pressure of the present complex was measured by a diaphragm type vapor pressure measuring device, it was found to be 199 Pa at 50 ° C., which indicates that the complex had a sufficient vapor pressure as an MOCVD material.
[0040]
Example 2
In Example 1, instead of vinyltrimethylsilane, vinyl-tert. In the same manner as in Example 1 except that 21.3 g (150 mmol) of -butyldimethylsilane was used, the target compound (1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedioxide) was obtained. Nato) copper (I) vinyl-tert. -Butyldimethylsilane was produced. As a result, the desired deep blue liquid was obtained in a yield of 69.1%. The target product was stored at room temperature, but did not decompose and was stable.
[0041]
The results of elemental analysis and 1 H-NMR were as follows.
C 16 H 28 O 2 F 3 SiCu (wt%)
Measurement value (C: 47.1, H: 6.8, F: 14.4, Cu: 15.7, Si: 7.1, K: not detected)
Calculated values (C: 47.9, H: 7.0, F: 14.2, Cu: 15.9, Si: 7.0, K: 0.0)
1 H-NMR (in C 6 D 6) δ0.095ppm (6H, s, SiCH 3), δ0.800ppm (9H, s, Si t Bu), δ1.07ppm (9H, s, t Bu (C = O )), Δ 4.10 ppm (3H, m, CH 2 CH-), δ 6.17 ppm (1 H, s, (C = O) CH (C = O))
The vapor pressure of the present complex was measured with a diaphragm type vapor pressure measuring apparatus, and it was found that the vapor pressure was 24.7 Pa at 50 ° C., indicating that the complex had a sufficient vapor pressure as an MOCVD material.
[0042]
Example 3
Under a nitrogen stream, 5.89 g (30.0 mmol) of 1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedione and 5.15 g of cuprous oxide were placed in a 100 ml Schlenk tube having a stirrer. (36.0 mmol), 15.0 g (150 mmol) of vinyltrimethylsilane, and 30 ml of molecular sieve were charged and reacted at room temperature for 22 hours with stirring. The molecular sieve and unreacted cuprous oxide were removed with a glass filter, and unreacted 1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedione and vinyltrimethylsilane were removed from the filtrate under reduced pressure. Under reduced conditions, 10.05 g of a dark blue liquid of 1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedionato) copper (I) vinyltrimethylsilane as a target substance (28. 0 mol). The yield was equivalent to 93.3% (based on hexanedione), an extremely high yield, and the effect of the production without solvent was confirmed. The target product was stored at room temperature, but did not decompose and was stable.
[0043]
The results of elemental analysis and 1 H-NMR of the target product were as follows.
C 13 H 22 O 2 F 3 SiCu (wt%)
Measurement value (C: 43.2, H: 6.2, F: 16.3, Cu: 17.4, Si: 7.9)
Calculated values (C: 43.5, H: 6.1, F: 15.9, Cu: 17.7, Si: 7.8)
1 H-NMR (in C 6 D 6 ) δ 0.088 ppm (9H, s, SiCH 3 ), δ 1.08 ppm (9 H, s, t Bu (C = O)), δ 4.10 ppm (3H, m, CH 2) CH-), δ 6.16 ppm (1H, s, (C = O) CH (C = O))
Comparative Example 1
In the same manner as in Example 1 except that 1,1,1-trifluoroacetylacetone was used instead of 1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedione in Example 1. Thus, a potassium salt of 1,1,1-trifluoroacetylacetone was obtained, and a dark blue liquid of (1,1,1-trifluoroacetylacetonato) copper (I) vinyltrimethylsilane, which was an object, was obtained. The yield was 57.3%. 1 H-NMR of the deep blue liquid is as follows.
[0044]
1 H-NMR (in C 6 D 6 ) δ 0.068 ppm (9H, s, SiCH 3 ), δ 1.74 ppm (3H, s, CH 3 (C = O)), δ 4.12 ppm (3H, broad, CH 2) = CH-), δ 5.73 ppm (1H, s, (C = O) CH (C = O))
However, when the deep blue liquid of the present 1,1,1-trifluoroacetylacetonato) copper (I) vinyltrimethylsilane was left at room temperature for 3 hours under a nitrogen atmosphere, a green solid and golden metallic copper were deposited. As a result, all the target liquids solidified. That is, it was recognized that the present copper complex was unstable and easily decomposed at room temperature, and was unsuitable as a MOCVD material.
[0045]
Comparative Example 2
An asymmetric β-diketone copper (I) complex was produced in the same manner as in Example 1 except that 28.5 g (150 mmol) of vinyltriethoxysilane was used instead of vinyltrimethylsilane. Only a green solid was obtained. Upon elemental analysis, the Cu content was 3.4 wt%. It was far from the calculated value of 14.2 wt%, and it was found that the target complex was not synthesized.
Comparative Example 3
In Example 1, 29.8 g (143 mmol) of 1,1,1,5,5,5-hexafluoroacetylacetone was used instead of 1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedione. ) And vinyl-tert. In place of vinyltrimethylsilane. In the same manner as in Example 1 except that 21.3 g (150 mmol) of -butyldimethylsilane was used, the target compound (1,1,1,5,5,5-hexafluoroacetylacetonato) copper (I ) Vinyl-tert. -Butyldimethylsilane was prepared. As a result, the desired dark green liquid was obtained in a yield of 83.0%. The target product was stored at room temperature, but was not decomposed and was stable.
[0046]
The results of elemental analysis and 1 H-NMR were as follows.
C 13 H 19 O 2 F 6 SiCu (wt%)
Measurement value (C: 37.4, H: 4.6, F: 28.0, Cu: 15.2, Si: 6.7, K not detected)
Calculated values (C: 37.8, H: 4.6, F: 27.6, Cu: 15.4, Si: 6.8, K: 0.0)
1 H-NMR (in C 6 D 6 ) δ 0.092 ppm (6H, s, SiCH 3 ), δ 0.79 ppm (9 H, s, Si-tBu), δ 4.20 ppm (3H, m, CH 2 CH-), δ 6.21 ppm (1H, s, (C = O) CH (C = O))
When the vapor pressure of the complex was measured by a diaphragm type vapor pressure measuring device, it was 2.2 Pa at 50 ° C., which was lower than that of the Cu (I) complex produced in Examples 1 to 3. Was.
[0047]
【The invention's effect】
According to the present invention, the following remarkable effects are obtained.
[0048]
As a first effect of the present invention, it is possible to provide a novel copper complex which has a lower fluorine content, is more stable and has a higher vapor pressure than a conventional fluorine-containing β-diketone copper (I) vinylsilane complex. Was. In particular, this complex is suitable as an MOCVD material for copper wiring.
[0049]
Second, in producing a copper (I) complex having an asymmetric β-diketone as a ligand, it has become possible to provide an extremely efficient and economical synthesis formulation.
Claims (5)
で示される銅錯体。The following general formula (1)
A copper complex represented by
下記一般式（３）のβジケトンと
酸化第一銅を反応させることを特徴とする銅錯体の製造方法。In the presence of a silyl group-substituted alkene of the following general formula (2),
Β diketone of the following general formula (3)
A method for producing a copper complex, comprising reacting cuprous oxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002346224A JP4254218B2 (en) | 2002-11-28 | 2002-11-28 | Copper complex having asymmetric β-diketone ligand and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002346224A JP4254218B2 (en) | 2002-11-28 | 2002-11-28 | Copper complex having asymmetric β-diketone ligand and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2004175755A true JP2004175755A (en) | 2004-06-24 |
| JP4254218B2 JP4254218B2 (en) | 2009-04-15 |
Family
ID=32707200
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002346224A Expired - Fee Related JP4254218B2 (en) | 2002-11-28 | 2002-11-28 | Copper complex having asymmetric β-diketone ligand and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4254218B2 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005170852A (en) * | 2003-12-11 | 2005-06-30 | Tosoh Corp | Copper complex and/or copper complex composition containing polysubstituted vinylsilane compound |
| US8623590B2 (en) | 2010-11-02 | 2014-01-07 | Shin-Etsu Chemical Co., Ltd. | Pattern forming process |
| US8632939B2 (en) | 2010-02-26 | 2014-01-21 | Shin-Etsu Chemical Co., Ltd. | Polymer, chemically amplified positive resist composition and pattern forming process |
| US8735046B2 (en) | 2010-11-29 | 2014-05-27 | Shin-Etsu Chemical Co., Ltd. | Positive resist composition and patterning process |
| US9017918B2 (en) | 2010-06-01 | 2015-04-28 | Shin-Etsu Chemical Co., Ltd. | Monomer, polymer, chemically amplified positive resist composition, and patterning process |
| US9091914B2 (en) | 2011-02-15 | 2015-07-28 | Shin-Etsu Chemical Co., Ltd. | Resist composition and patterning process |
| US9360753B2 (en) | 2011-07-25 | 2016-06-07 | Shin-Etsu Chemical Co., Ltd. | Resist composition and patterning process |
-
2002
- 2002-11-28 JP JP2002346224A patent/JP4254218B2/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005170852A (en) * | 2003-12-11 | 2005-06-30 | Tosoh Corp | Copper complex and/or copper complex composition containing polysubstituted vinylsilane compound |
| JP4529434B2 (en) * | 2003-12-11 | 2010-08-25 | 東ソー株式会社 | Copper complex and copper complex composition comprising a polysubstituted vinylsilane compound |
| US8632939B2 (en) | 2010-02-26 | 2014-01-21 | Shin-Etsu Chemical Co., Ltd. | Polymer, chemically amplified positive resist composition and pattern forming process |
| US9017918B2 (en) | 2010-06-01 | 2015-04-28 | Shin-Etsu Chemical Co., Ltd. | Monomer, polymer, chemically amplified positive resist composition, and patterning process |
| US8623590B2 (en) | 2010-11-02 | 2014-01-07 | Shin-Etsu Chemical Co., Ltd. | Pattern forming process |
| US8735046B2 (en) | 2010-11-29 | 2014-05-27 | Shin-Etsu Chemical Co., Ltd. | Positive resist composition and patterning process |
| US9091914B2 (en) | 2011-02-15 | 2015-07-28 | Shin-Etsu Chemical Co., Ltd. | Resist composition and patterning process |
| US9360753B2 (en) | 2011-07-25 | 2016-06-07 | Shin-Etsu Chemical Co., Ltd. | Resist composition and patterning process |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4254218B2 (en) | 2009-04-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3593051B2 (en) | Volatile precursors for deposition of metals and metal-containing films | |
| JP4414397B2 (en) | Volatile metal β-ketoiminate complex | |
| US6803477B2 (en) | Magnesium mediated preparation of fluorinated alkyl silanes | |
| JP4254218B2 (en) | Copper complex having asymmetric β-diketone ligand and method for producing the same | |
| JP4660924B2 (en) | Stabilized copper complex and method for producing the same | |
| US5453528A (en) | Optimized process for inert fluorinated silanes | |
| RU2181725C2 (en) | Copper (i)-organic compounds and method of copper film precipitation by their using | |
| JP4363052B2 (en) | Copper complex having asymmetric β-diketone ligand and method for producing the same | |
| JP4529434B2 (en) | Copper complex and copper complex composition comprising a polysubstituted vinylsilane compound | |
| JP4125728B2 (en) | Monovalent copper complex | |
| JP4120925B2 (en) | Copper complex and method for producing copper-containing thin film using the same | |
| TW202321268A (en) | Synthesis of fluoroalkyl tin precursors | |
| JP4622098B2 (en) | Stabilized silicon-containing alkene copper complex and method for producing the same | |
| JP3282392B2 (en) | Organocopper compounds for copper thin film formation by metalorganic chemical vapor deposition with high vapor pressure | |
| JP2004059544A (en) | Substituted cyclopentadienyl copper complex and method for producing the same | |
| JP6565448B2 (en) | Method for producing aluminum oxide film and raw material for producing aluminum oxide film | |
| TWI316970B (en) | Dicopper(i) oxalate complexes as precursor substances for the deposition of metallic copper | |
| JP2768250B2 (en) | Organic silver compounds for forming silver thin films by metalorganic chemical vapor deposition with high vapor pressure | |
| JP2762905B2 (en) | Organic silver compounds for forming silver thin films by metalorganic chemical vapor deposition with high vapor pressure | |
| JP2004214161A (en) | Material for insulating film containing organic silane compound, its manufacturing method, and semiconductor device | |
| CN100415752C (en) | Insulating film material containing an organic silane compound, its production method and semiconductor device | |
| JP3284689B2 (en) | Organocopper compounds for copper thin film formation by metalorganic chemical vapor deposition with high vapor pressure | |
| WO2023012494A1 (en) | Method for the silylation of a c-h bond with a silylated diazene | |
| JP2009023966A (en) | Method for producing alkoxy-substituted cyclotrisiloxane compound | |
| JP2001048887A (en) | Tetrakis(diaryl-silyl)benzene and production of the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20050926 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20080708 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20080903 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20081007 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20081128 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20090106 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20090119 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120206 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120206 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120206 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130206 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140206 Year of fee payment: 5 |
|
| LAPS | Cancellation because of no payment of annual fees |