CN102753724A - Material for forming ruthenium film and method for forming ruthenium film - Google Patents
Material for forming ruthenium film and method for forming ruthenium film Download PDFInfo
- Publication number
- CN102753724A CN102753724A CN2011800088816A CN201180008881A CN102753724A CN 102753724 A CN102753724 A CN 102753724A CN 2011800088816 A CN2011800088816 A CN 2011800088816A CN 201180008881 A CN201180008881 A CN 201180008881A CN 102753724 A CN102753724 A CN 102753724A
- Authority
- CN
- China
- Prior art keywords
- ruthenium
- film
- ruthenium film
- phosphine
- trifluoro
- 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
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 75
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 239000000463 material Substances 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims description 31
- 150000001875 compounds Chemical class 0.000 claims abstract description 21
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 18
- 125000005843 halogen group Chemical group 0.000 claims abstract description 13
- 150000002430 hydrocarbons Chemical group 0.000 claims abstract description 8
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims abstract description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 34
- 230000015556 catabolic process Effects 0.000 claims description 10
- 238000006731 degradation reaction Methods 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 239000012808 vapor phase Substances 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 239000011159 matrix material Substances 0.000 claims description 9
- 125000001188 haloalkyl group Chemical group 0.000 claims description 5
- 150000003303 ruthenium Chemical class 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 8
- 239000001301 oxygen Substances 0.000 abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 abstract description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract 2
- 150000008282 halocarbons Chemical group 0.000 abstract 1
- 239000007800 oxidant agent Substances 0.000 abstract 1
- WKFBZNUBXWCCHG-UHFFFAOYSA-N phosphorus trifluoride Chemical compound FP(F)F WKFBZNUBXWCCHG-UHFFFAOYSA-N 0.000 description 37
- ICHKQLWOZTXJLX-UHFFFAOYSA-N [Ru].FP(F)F Chemical compound [Ru].FP(F)F ICHKQLWOZTXJLX-UHFFFAOYSA-N 0.000 description 34
- HDMBQRSQOUNNSO-UHFFFAOYSA-N ruthenium;trimethylphosphane Chemical compound [Ru].CP(C)C HDMBQRSQOUNNSO-UHFFFAOYSA-N 0.000 description 26
- 238000006243 chemical reaction Methods 0.000 description 20
- 239000007789 gas Substances 0.000 description 20
- 238000002309 gasification Methods 0.000 description 18
- 239000000758 substrate Substances 0.000 description 18
- 229910052751 metal Inorganic materials 0.000 description 16
- 239000002184 metal Substances 0.000 description 16
- 238000003860 storage Methods 0.000 description 15
- 238000009834 vaporization Methods 0.000 description 15
- 230000008016 vaporization Effects 0.000 description 15
- 229910052802 copper Inorganic materials 0.000 description 13
- 239000010949 copper Substances 0.000 description 13
- 239000012299 nitrogen atmosphere Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 12
- 239000001257 hydrogen Substances 0.000 description 12
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- 229910052731 fluorine Inorganic materials 0.000 description 9
- 150000003304 ruthenium compounds Chemical class 0.000 description 9
- YAYGSLOSTXKUBW-UHFFFAOYSA-N ruthenium(2+) Chemical compound [Ru+2] YAYGSLOSTXKUBW-UHFFFAOYSA-N 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 229910052801 chlorine Inorganic materials 0.000 description 8
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 8
- 125000003963 dichloro group Chemical group Cl* 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- -1 isobutyl- Chemical group 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 238000013112 stability test Methods 0.000 description 7
- 230000002194 synthesizing effect Effects 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 230000004888 barrier function Effects 0.000 description 6
- 125000001153 fluoro group Chemical group F* 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 230000006978 adaptation Effects 0.000 description 5
- 230000008676 import Effects 0.000 description 5
- 238000007747 plating Methods 0.000 description 5
- IQRJQJHIBJHUIP-UHFFFAOYSA-N ruthenium;triethylphosphane Chemical compound [Ru].CCP(CC)CC IQRJQJHIBJHUIP-UHFFFAOYSA-N 0.000 description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 125000001309 chloro group Chemical group Cl* 0.000 description 4
- 230000006837 decompression Effects 0.000 description 4
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 4
- 229910052740 iodine Inorganic materials 0.000 description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- HQQLMNHRXBTVQR-UHFFFAOYSA-N ruthenium(2+) trifluorophosphane Chemical compound [Ru+2].FP(F)F HQQLMNHRXBTVQR-UHFFFAOYSA-N 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- YWWDBCBWQNCYNR-UHFFFAOYSA-N trimethylphosphine Chemical compound CP(C)C YWWDBCBWQNCYNR-UHFFFAOYSA-N 0.000 description 4
- ZRNSSRODJSSVEJ-UHFFFAOYSA-N 2-methylpentacosane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCC(C)C ZRNSSRODJSSVEJ-UHFFFAOYSA-N 0.000 description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- PQIOSYKVBBWRRI-UHFFFAOYSA-N methylphosphonyl difluoride Chemical group CP(F)(F)=O PQIOSYKVBBWRRI-UHFFFAOYSA-N 0.000 description 3
- NBVXSUQYWXRMNV-UHFFFAOYSA-N monofluoromethane Natural products FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000012797 qualification Methods 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 3
- HITROERJXNWVOI-SOFGYWHQSA-N (5e)-octa-1,5-diene Chemical compound CC\C=C\CCC=C HITROERJXNWVOI-SOFGYWHQSA-N 0.000 description 2
- XWJBRBSPAODJER-UHFFFAOYSA-N 1,7-octadiene Chemical compound C=CCCCCC=C XWJBRBSPAODJER-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- LELIHYATYYMZBR-UHFFFAOYSA-N [Ru].CP(C)C.[Ru] Chemical group [Ru].CP(C)C.[Ru] LELIHYATYYMZBR-UHFFFAOYSA-N 0.000 description 2
- 239000003708 ampul Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 125000001246 bromo group Chemical group Br* 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- FZHCFNGSGGGXEH-UHFFFAOYSA-N ruthenocene Chemical compound [Ru+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 FZHCFNGSGGGXEH-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 2
- APPOKADJQUIAHP-GGWOSOGESA-N (2e,4e)-hexa-2,4-diene Chemical compound C\C=C\C=C\C APPOKADJQUIAHP-GGWOSOGESA-N 0.000 description 1
- GDDAJHJRAKOILH-QFXXITGJSA-N (2e,5e)-octa-2,5-diene Chemical compound CC\C=C\C\C=C\C GDDAJHJRAKOILH-QFXXITGJSA-N 0.000 description 1
- AHAREKHAZNPPMI-AATRIKPKSA-N (3e)-hexa-1,3-diene Chemical compound CC\C=C\C=C AHAREKHAZNPPMI-AATRIKPKSA-N 0.000 description 1
- FMAMSYPJXSEYSW-VOTSOKGWSA-N (4e)-hepta-1,4-diene Chemical compound CC\C=C\CC=C FMAMSYPJXSEYSW-VOTSOKGWSA-N 0.000 description 1
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- ZGXMNEKDFYUNDQ-GQCTYLIASA-N (5e)-hepta-1,5-diene Chemical compound C\C=C\CCC=C ZGXMNEKDFYUNDQ-GQCTYLIASA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 description 1
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 1
- 125000004206 2,2,2-trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 1
- AIDLAEPHWROGFI-UHFFFAOYSA-N 2-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=C(C(O)=O)C=CC=C1C(O)=O AIDLAEPHWROGFI-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 241000588731 Hafnia Species 0.000 description 1
- AYDQIZKZTQHYIY-UHFFFAOYSA-N OC(=O)C1(C)CC(C(O)=O)=CC=C1 Chemical compound OC(=O)C1(C)CC(C(O)=O)=CC=C1 AYDQIZKZTQHYIY-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- KZQZHJYUKYNVLN-UHFFFAOYSA-N [Ru].C(C)P(CC)CC.[Ru] Chemical group [Ru].C(C)P(CC)CC.[Ru] KZQZHJYUKYNVLN-UHFFFAOYSA-N 0.000 description 1
- UWVAEWDGBSHEKV-UHFFFAOYSA-N [Ru].FP(F)F.[Ru] Chemical group [Ru].FP(F)F.[Ru] UWVAEWDGBSHEKV-UHFFFAOYSA-N 0.000 description 1
- UYDFJFYODBADMH-UHFFFAOYSA-N [Ru]C1=CC=CCC1 Chemical compound [Ru]C1=CC=CCC1 UYDFJFYODBADMH-UHFFFAOYSA-N 0.000 description 1
- WOIHABYNKOEWFG-UHFFFAOYSA-N [Sr].[Ba] Chemical compound [Sr].[Ba] WOIHABYNKOEWFG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 125000000950 dibromo group Chemical group Br* 0.000 description 1
- 125000004772 dichloromethyl group Chemical group [H]C(Cl)(Cl)* 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 1
- GEAWFZNTIFJMHR-UHFFFAOYSA-N hepta-1,6-diene Chemical compound C=CCCCC=C GEAWFZNTIFJMHR-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000001272 nitrous oxide Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
- H01L21/285—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation
- H01L21/28506—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers
- H01L21/28512—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table
- H01L21/28556—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table by chemical means, e.g. CVD, LPCVD, PECVD, laser CVD
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
- H01L21/76841—Barrier, adhesion or liner layers
- H01L21/76871—Layers specifically deposited to enhance or enable the nucleation of further layers, i.e. seed layers
- H01L21/76873—Layers specifically deposited to enhance or enable the nucleation of further layers, i.e. seed layers for electroplating
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
- H01L21/76841—Barrier, adhesion or liner layers
- H01L21/76843—Barrier, adhesion or liner layers formed in openings in a dielectric
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Vapour Deposition (AREA)
- Electrodes Of Semiconductors (AREA)
Abstract
Disclosed is a material for forming a ruthenium film, which is easily decomposed in the absence of an oxidizing agent such as oxygen. Specifically disclosed is a material for forming a ruthenium film, which contains a compound represented by formula (1). Ru(PR1 3)l(L1)m(L2)n (1) (In formula (1), R1s each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1-4 carbon atoms or a halogenated hydrocarbon group having 1-4 carbon atoms; L1 represents a hydrogen atom or a halogen atom; L2 represents an unsaturated hydrocarbon compound having at least two double bonds and 4-10 carbon atoms; l represents an integer of 1-5; m represents an integer of 0-4; and n represents an integer of 0-2. In this connection, l + m + 2n is 5 or 6).
Description
Technical field
The present invention relates to the ruthenium film forms with material and ruthenium film formation method.
Background technology
With DRAM (Dynamic Random Access Memory) is that the semiconductor devices of representative is accompanied by its highly integrated and miniaturization and must changes each metallic membrane of constitution equipment and the material of metal oxide film.
Wherein, require improvement conductive metal film in the multilayer wiring purposes in semiconductor devices, carry out to the copper wiring conversion that novel conductive property is high.From the purpose that improves this copper wiring electroconductibility, in the layer insulation mould material of multilayer wiring, use advanced low-k materials (Low-k material).But the Sauerstoffatom that in this advanced low-k materials, contains is introduced in easily to produce in the copper wiring and makes its electroconductibility reduce this problem.Therefore, from the purpose that prevents from the oxygen migration of advanced low-k materials, studying the technology that between advanced low-k materials and copper wiring, forms barrier film.As in this barrier film purposes, use, be difficult to introduce from the material of the oxygen of medium layer and utilize and do material processed easily at quarter, the metal Ru film is gazed at.And then, adopting plating method to imbed being set in the embrane method of above-mentioned copper wiring, consider that from the purpose that satisfies above-mentioned barrier film and plating growing film both sides effect simultaneously metal Ru is gazed at.
In addition, in the electrical condenser of semiconductor devices, as the electrode materials of the such high dielectric constant material of aluminum oxide, tantalum pentoxide, hafnia, barium strontium (BST), the metal Ru film is gazed at owing to its high oxidation resistance voltinism and high conductivity.
In the formation of above-mentioned metal Ru film, in the past adopt sputtering methods more, but in recent years as for miniaturization, the filmization of structure, improve the correspondence of mass productivity, studying the chemical vapor-phase growing method.
But with regard to the metallic membrane that general employing chemical vapor-phase growing method forms, configuration of surface such as the state of aggregation of crystallite is sparse is poor; As the means that are used to solve this type form problem; Research uses three (2,2,6 in the chemical vapor-phase growing material; 6-tetramethyl--3,5-heptadione acid) ruthenium, ruthenocene, two (alkyl cyclopentadienyl) ruthenium, three carbonyls (cyclohexadienyl) ruthenium etc. are (with reference to patent documentation 1~5.)。
And then, when in manufacturing process, using these chemical vapor-phase growing materials, from the deterioration that prevents metal Ru film adjacent material film formation process with stablize its purpose of creating conditions and consider, need the good storage stability of material.But existence such as existing ruthenocene, two (alkyl cyclopentadienyl) ruthenium produce and to be caused by oxygen blended influence in the film formation process in short period of time adjacent material oxidation and this problem of performance degradation of following it.In addition, when in film formation process, not mixing oxygen, exist the ruthenium film to be difficult to this problem of film forming.
On the other hand, to require the ruthenium film be high purity, as the excellent performance of barrier film and plating growing film and excellent for the adaptation of substrate.
Patent documentation 1: japanese kokai publication hei 6-283438 communique
Patent documentation 2: japanese kokai publication hei 11-35589 communique
Patent documentation 3: TOHKEMY 2002-114795 communique
Patent documentation 4: TOHKEMY 2002-212112 communique
Patent documentation 5: TOHKEMY 2006-241557 communique
Summary of the invention
The present invention is in view of the above problems and the technical scheme of accomplishing; Its purpose is, also can decompose easily, can short period of time ground form with material and the ruthenium film formation method of using this material with high purity and to the film forming ruthenium film of the excellent ruthenium film of the adaptation of substrate even provide in the presence of oxygenants such as oxygen are non-.
In order to achieve the above object, contriver of the present invention etc. further investigate, and find can achieve the above object through the compound that adopts following formula (1) expression, and the present invention is accomplished.
That is, the present invention provides following [ 1 ]~[ 6 ].
[ 1 ] material is used in the ruthenium film formation that contains the compound of following formula (1) expression.
Ru(PR
1 3)
l(L
1)
m(L
2)
n (1)
(in the above-mentioned formula (1), R
1Independently of one another for Wasserstoffatoms, halogen atom, carbonatoms are that 1~4 alkyl or carbonatoms are 1~4 halo alkyl, L
1Be Wasserstoffatoms or halogen atom, L
2Be that carbonatoms with at least two two keys is 4~10 unsaturated hydrocarbon compound, l is 1~5 integer, and m is 0~4 integer, and n is 0~2 integer.Wherein, l+m+2n=5 or 6.)
[ 2 ] use material according to above-mentioned [ 1 ] described ruthenium film formation, be used for the chemical vapor-phase growing method.
[ 3 ] a kind of ruthenium film formation method wherein, is used the described ruthenium film in above-mentioned [ 1 ] or [ 2 ] to form and is used material.
[ 4 ] a kind of ruthenium film formation method comprises that above-mentioned [ 2 ] described ruthenium film is formed the ruthenium film formation that supplies on the matrix with material to be supplied with operation and this ruthenium film formation is formed operation with the film that the material thermal degradation is formed on the above-mentioned matrix ruthenium film with material.
[ 5 ] according to above-mentioned [ 4 ] described ruthenium film formation method, wherein, the temperature that above-mentioned film forms the thermal degradation in the operation is 100 ℃~800 ℃.
[ 6 ] according to above-mentioned [ 4 ] or [ 5 ] described ruthenium film formation method, wherein, the thermal degradation that above-mentioned film forms in the operation is carried out in non-active gas or reducing gas.
Ruthenium film of the present invention forms with material and in the presence of oxygenants such as oxygen are non-, also can decompose easily and form the ruthenium film.Therefore, adjacent material oxidation and be accompanied by its performance degradation possible little takes place.
In addition, utilize ruthenium film of the present invention to form and use material, can be with the short period of time and easily obtain the few high purity high-quality ruthenium film of residual impurity amount.This ruthenium film is as the excellent performance of barrier film and plating growing film, and also excellent for the adaptation of substrate.
Embodiment
Below, the present invention is at length explained.
Ruthenium film formation of the present invention contains the compound of following formula (1) expression with material and forms.
Ru(PR
1 3)
l(L
1)
m(L
2)
n (1)
In the above-mentioned formula (1), R
1Be that Wasserstoffatoms, halogen atom, carbonatoms are that 1~4 alkyl or carbonatoms are 1~4 halo alkyl independently of one another; Be preferably halogen atom, carbonatoms and be 1~4 alkyl or carbonatoms and be 1~4 halo alkyl, more preferably halogen atom.
At R
1In, can enumerate fluorine atom, chlorine atom, bromine atoms, iodine atom as halogen atom, be preferably fluorine atom, chlorine atom, more preferably fluorine atom.
In addition, at R
1In, be 1~4 alkyl as carbonatoms, can enumerate methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, be preferably methyl, ethyl, n-propyl, sec.-propyl, the tertiary butyl, more preferably methyl, ethyl.
In addition, at R
1In, be 1~4 halo alkyl as carbonatoms, be preferably and fluoridize alkyl, chlorination alkyl, bromination alkyl, more preferably fluoridize alkyl.
Can enumerate chloromethyl, dichloromethyl, trichloromethyl, methyl fluoride, difluoromethyl, trifluoromethyl, 2 particularly; 2; 2-trifluoroethyl, pentafluoroethyl group, perfluor n-propyl, perfluor sec.-propyl, perfluor normal-butyl, perfluor isobutyl-, the perfluor tertiary butyl are preferably methyl fluoride, difluoromethyl, trifluoromethyl, 2,2; 2-trifluoroethyl, pentafluoroethyl group, perfluor n-propyl, perfluor sec.-propyl, the perfluor tertiary butyl; More preferably methyl fluoride, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, pentafluoroethyl group.
In the general formula (1), L
1Be Wasserstoffatoms or halogen atom, be preferably Wasserstoffatoms.
L
1When being halogen atom,, fluorine atom, chlorine atom, bromine atoms, iodine atom be can enumerate, fluorine atom, chlorine atom, more preferably fluorine atom are preferably as this halogen atom.
In addition, in the general formula (1), L
2Be that carbonatoms with at least two two keys is 4~10 unsaturated hydrocarbon compound.
Obtain to be easy to viewpoint from compound and consider that the double key number amount is preferably two.In this case, unsaturated hydrocarbon compound can be a conjugated diene compound, also can be non-conjugated diene compound.
The carbonatoms of above-mentioned unsaturated hydrocarbon compound is 4~10, is preferably 5~8.
Can enumerate 1,3-butadiene, 2 particularly, 3-dimethyl--1,3-butadiene, 1,3-pentadiene, 1; 5-hexadiene, 1,4-hexadiene, 1,3-hexadiene, 2,4-hexadiene, 3-methyl isophthalic acid, 3-pentadiene, 2-methyl isophthalic acid; 4-pentadiene, 1,6-heptadiene, 1,5-heptadiene, 1,4-heptadiene, 1,7-octadiene, 1; 6-octadiene, 1,5-octadiene, 1, chain diene such as 4-octadiene, cyclopentadiene, 1,5-cyclooctadiene, 1; 3-cyclooctadiene, 1,1,2, cyclic dienes such as 5-norbornadiene.
In addition, in the general formula (1), l is 1~5 integer, considers from high this viewpoint of vapour pressure of compound, is preferably 3~5 integer.
In addition, in the general formula (1), m is 0~4 integer, considers from low this viewpoint of fusing point of compound, is preferably 0~3 integer, more preferably 0~2 integer.
In addition, in the general formula (1), n is 0~2 integer, considers from the viewpoint that forms the high ruthenium film of high-quality and purity, is preferably 0 or 1, more preferably 0.
In addition, l+m+2n=5 or 6.
The synthesis method of the compound of above-mentioned general formula (1) expression for example can be enumerated and comprise and make the middle PR of ruthenium trichloride and above-mentioned general formula (1)
1 3The method of the operation that the compound of expression reacts.In above-mentioned operation, also can make as required to be selected from least a compound in hydrogen, fluorine, chlorine, bromine and the iodine and to be selected from L in the above-mentioned general formula (1)
2The carbonatoms with at least two two keys of expression is that at least a compound in 4~10 the unsaturated hydrocarbon compound reacts.
Above-mentioned reaction is preferably carried out in the presence of catalyzer, as catalyzer, for example can enumerate copper, zinc etc.
As temperature of reaction, not special the qualification, but be preferably 50~400 ℃, more preferably 100~350 ℃, further be preferably 120 ℃~300 ℃.
In addition, as the pressure in when reaction, not special the qualification makes trifluoro phosphine, hydrogen, fluorine, chlorine etc. under standard conditions during for the compound reaction of gas, be generally 10~1000 air pressure (below be also referred to as " atm ".), be preferably 50~800 air pressure, more preferably 100~600 air pressure.
As the concrete example of the compound of above-mentioned general formula (1) expression, for example can enumerate:
As the compound of l=5, m=0, n=0, five (trifluoro phosphine) rutheniums (0), five (trichlorine phosphine) rutheniums (0), five (trimethyl-phosphine) ruthenium (0), five (triethyl phosphine) ruthenium ruthenium atom valencys such as (0) are 0 ruthenium compound;
Compound as l=3, m=0, n=1; (η-1) three (trifluoro phosphine) ruthenium (0), (η-1) three (trimethyl-phosphine) ruthenium (0), (1; The 5-cyclooctadiene) three (trifluoro phosphine) rutheniums (0), (1; The 5-cyclooctadiene) three (trimethyl-phosphine) ruthenium (0), (η-1,6-heptadiene) three (trifluoro phosphine) rutheniums (0), (η-1,6-heptadiene) three (trimethyl-phosphine) ruthenium (0), (η-1; The 7-octadiene) three (trifluoro phosphine) rutheniums (0), (η-1,7-octadiene) three (trimethyl-phosphine) ruthenium ruthenium atom valencys such as (0) are 0 ruthenium compound;
As the compound of l=4, m=2, n=0, four (trifluoro phosphine) dihydro rutheniums (II), (difluoro) four (trifluoro phosphine) ruthenium (II), (dichloro) four (trifluoro phosphine) ruthenium (II), four (trimethyl-phosphine) dihydro ruthenium (II), (difluoro) four (trimethyl-phosphine) ruthenium (II), (dichloro) four (trimethyl-phosphine) ruthenium ruthenium atom valencys such as (II) are 2 ruthenium compound;
As the compound of l=3, m=3, n=0, three (trifluoro phosphine) three hydrogen rutheniums (III), (trifluoro) three (trifluoro phosphine) ruthenium ruthenium atom valencys such as (III) are 3 ruthenium compound;
As the compound of l=2, m=4, n=0, two (trifluoro phosphine) tetrahydrochysene rutheniums (IV), (tetrafluoro) two (trifluoro phosphine) rutheniums (IV), (tetrachloro) two (trifluoro phosphine) rutheniums (IV), (trifluoro) four (trifluoro phosphine) hydrogen ruthenium (IV), (difluoro) four (trifluoro phosphine) dihydro ruthenium (IV), (dibromo) four (trifluoro phosphine) dihydro ruthenium (IV), (fluorine) four (trifluoro phosphine) three hydrogen rutheniums (IV), (iodine) four (trifluoro phosphine) three hydrogen ruthenium ruthenium atoms such as (IV) valencys are 3 ruthenium compound etc.
These compounds can perhaps form mixing more than 2 kinds separately and use with material as the ruthenium film.1 kind of compound of preferred use separately forms as the ruthenium film uses material.
Ruthenium film formation method of the present invention is used above-mentioned ruthenium film to form and is used material.
Ruthenium film formation method of the present invention is used above-mentioned ruthenium film to form and is used material, in addition, also can use itself known method, for example can adopt following chemical vapor-phase growing method (method that comprises following operation (1) and operation (2)) to implement.
Ruthenium film formation of the present invention is supplied on the matrix (for example substrate) with material, then, the ruthenium film that supplies on the matrix is formed use the material thermal degradation, thereby on matrix, form the ruthenium film.Particularly; (1) ruthenium film of the present invention is formed with material and perhaps evaporate, its vapour or evaporant are deposited on the matrix (for example substrate), then in decompression and heating gasified; (2) stores that obtains is heated make its thermolysis, the ruthenium film is formed on matrix.In addition, in above-mentioned operation (1), even form the decomposition with material with ruthenium film of the present invention, also can not weaken effect of the present invention, above-mentioned operation (1) and above-mentioned operation (2) can be carried out simultaneously.
As can be at the body material of this use, for example can use suitable material such as glass, silicon semiconductor, quartz, metal, MOX, synthetic resins, but preferably to the material with the temperature tolerance of ruthenium compound pyrolysated operation.
In above-mentioned operation (1), make the temperature of ruthenium compound gasification or evaporation be preferably-100~350 ℃, further be preferably-80~200 ℃, be preferably-60~150 ℃ especially.
In above-mentioned operation (1), the reduced pressure when the ruthenium compound gasification is perhaps evaporated is preferably below the 1000Pa, further is preferably below the 100Pa, is preferably below the 50Pa especially.The lower value of this reduced pressure is not special to be limited, but considers from the viewpoint of reliever performance, is generally 1Pa.
In above-mentioned operation (2), make the temperature of ruthenium compound thermal degradation be preferably 100~800 ℃, more preferably 100~600 ℃, further be preferably 180~450 ℃, further be preferably 200~420 ℃, be preferably 250~410 ℃ especially.
Chemical vapor-phase growing method of the present invention all can be implemented in the presence of non-active gas and under the arbitrary condition in not, in addition, in the presence of reducing gas and under the arbitrary condition in not, all can implement.But arbitrary side or two sides in preferred non-active gas and the reducing gas exist.
As non-active gas, for example can enumerate nitrogen, argon gas, helium etc. at this.In addition, as reducing gas, for example can enumerate hydrogen, ammonia etc.In addition, chemical vapor-phase growing method of the present invention also can be implemented under the coexistence of oxidizing gas.At this,, for example can enumerate oxygen, carbon monoxide, Nitrous Oxide etc. as oxidizing gas.
Especially the purpose that reduces from the amount that makes impurity in the film forming ruthenium film preferably makes these reducing gas coexistences.When making the reducing gas coexistence, the ratio of reducing gas is preferably 1~100 mole of % in the atmosphere, more preferably 3~100 moles of %.
The ratio of oxidizing gas is preferably 10 moles below the % in the atmosphere, more preferably 1 mole below the %, is preferably 0.1 mole especially below the %.
Above-mentioned operation (2) in the chemical vapor-phase growing method of the present invention is depressed, all can be implemented under the normal pressure and under the arbitrary condition under the decompression adding.Wherein, preferably under normal pressure or under the decompression, implement, further preferably under the pressure below the 15000Pa, implement.
Ruthenium film of the present invention forms and preferably under non-active gas atmosphere, preserves with material.As non-active gas, for example can enumerate nitrogen, argon gas, helium etc.
The ruthenium film purity that obtains as stated and electroconductibility are high, can in the barrier film of for example cloth line electrode, plating growing film, electrode for capacitors etc., preferably use.
Embodiment
Below, through embodiment the present invention is described particularly, but the present invention does not receive any qualification of these embodiment.
Synthesizing of [ synthetic example 1 ] five (trifluoro phosphine) rutheniums (0)
Making the reactor drum that ruthenium trichloride 5.03g, copper 10.08g are housed is vacuum, imports the trifluoro phosphine until reaching 500atm, heats 15 hours down at 250 ℃.Reaction is carried out drying under reduced pressure, thereby is removed the trifluoro phosphine after accomplishing after with the solution cool to room temperature.The solid that obtains is carried out sublimation purifying under 30 ℃, 0.013atm (10Torr), obtain to be five (trifluoro phosphine) ruthenium (0) 7.80g of white solid thus.Yield is 60 weight %.
Synthesizing of [ synthetic example 2 ] five (triethyl phosphine) ruthenium (0)
With the ampoule tube sealing that ruthenium trichloride 5.03g, copper 10.08g, triethyl phosphine 10mL are housed, heated 24 hours down at 220 ℃.Reaction after with the solution cool to room temperature, is filtered under nitrogen atmosphere after accomplishing.Filtrating is carried out drying under reduced pressure remove triethyl phosphine, thereby obtain to be five (triethyl phosphine) ruthenium (0) 3.67g of white solid.Yield is 22 weight %.
Synthesizing of [ synthetic example 3 ] (1, the 5-cyclooctadiene) three (trifluoro phosphine) rutheniums (0)
Make ruthenium trichloride 5.03g, copper 10.08g, 1 are housed, be vacuum after the reactor drum of 5-cyclooctadiene 50mL is being cooled to-78 ℃, import the trifluoro phosphine, heated 72 hours down at 180 ℃ until reaching 400atm.Reaction after with the solution cool to room temperature, is filtered under nitrogen atmosphere after accomplishing.After filtrating is carried out drying under reduced pressure, under nitrogen atmosphere, carry out alumina column chromatography and (launch solvent: Anaesthetie Ether),, thereby obtain to be (1, the 5-cyclooctadiene) three (trifluoro phosphine) ruthenium (0) 1.71g of weak yellow liquid the solution concentration that obtains.Yield is 15 weight %.
Synthesizing of [ synthetic example 4 ] (1, the 5-cyclooctadiene) three (trimethyl-phosphine) ruthenium (0)
Ruthenium trichloride 5.03g, copper 10.08g, 1 will be housed, and the ampoule tube sealing of 5-cyclooctadiene 20mL, trimethyl-phosphine 10mL heated 90 hours down at 160 ℃.Reaction after with the solution cool to room temperature, is filtered under nitrogen atmosphere after accomplishing.After filtrating is carried out drying under reduced pressure, under nitrogen atmosphere, carry out alumina column chromatography and (launch solvent: Anaesthetie Ether),, thereby obtain to be (1, the 5-cyclooctadiene) three (trimethyl-phosphine) ruthenium (0) 0.63g of weak yellow liquid the solution concentration that obtains.Yield is 6 weight %.
Synthesizing of [ synthetic example 5 ] four (trifluoro phosphine) dihydro rutheniums (II)
Making the reactor drum that ruthenium trichloride 5.03g, copper 10.08g are housed is vacuum, imports trifluoro phosphine 300atm, hydrogen 100atm, heats 15 hours down at 270 ℃.Reaction is carried out drying under reduced pressure, thereby is removed trifluoro phosphine and hydrogen after accomplishing after with the solution cool to room temperature.The liquid that obtains is filtered under nitrogen atmosphere, at room temperature reduce pressure to steam and stay, obtain to be four (trifluoro phosphine) dihydro ruthenium (II) 7.68g of colourless transparent liquid thus with 0.013atm (10Torr).Yield is 70 weight %.
Synthesizing of [ synthetic example 6 ] (1, the 5-octadiene) three (trifluoro phosphine) rutheniums (0)
Make ruthenium trichloride 5.03g, copper 10.08g, 1 are housed, be vacuum after the reactor drum of 5-octadiene 50mL is being cooled to-78 ℃, import the trifluoro phosphine, heated 100 hours down at 120 ℃ until reaching 400atm.Reaction after with the solution cool to room temperature, is filtered under nitrogen atmosphere after accomplishing.After filtrating is carried out drying under reduced pressure, under nitrogen atmosphere, carry out alumina column chromatography and (launch solvent: Anaesthetie Ether),, thereby obtain to be (1, the 5-octadiene) three (trifluoro phosphine) ruthenium (0) 1.14g of weak yellow liquid the solution concentration that obtains.Yield is 10 weight %.
Synthesizing of [ synthetic example 7 ] (dichloro) four (trifluoro phosphine) ruthenium (II)
Making the reactor drum that ruthenium trichloride 5.03g, copper 10.08g are housed is vacuum, imports trifluoro phosphine 300atm, chlorine 100atm, heats 15 hours down at 250 ℃.Reaction is carried out drying under reduced pressure, thereby is removed trifluoro phosphine and chlorine after accomplishing after with the solution cool to room temperature.The liquid that obtains is filtered under nitrogen atmosphere, at room temperature reduce pressure to steam and stay, obtain to be (dichloro) four of weak yellow liquid (trifluoro phosphine) ruthenium (II) 4.83g thus with 10torr.Yield is 41 weight %.
In following examples, adopt the probe resistance rate tester (model: RT-80/RG-80) measure of Napson corporate system than resistance.Thickness adopts the oblique incidence x-ray analysis equipment (model: X'Pert MRD) measure of Philips corporate system.ESCA spectrum adopts the tester (model: JPS80) measure of NEC's corporate system.In addition, for adaptation, be that benchmark adopts checker to test to estimate with JIS K-5400, when not observing substrate and ruthenium film fully and peel off for " zero ", when observing substrate and ruthenium film and peel off, be " * ".
[ embodiment 1 ]
(1) formation of ruthenium film
Weighing is placed in the quartzy system reaction vessel by five (trifluoro phosphine) ruthenium (0) 0.05g that synthetic example 1 obtains in quartz system ship type container in oxide gas.In reaction vessel air-flow downflow direction side near placement have the silicon wafer of heat oxide film, at room temperature hydrogen was flowed 20 minutes in reaction vessel with 300mL/ minute flow.Afterwards, hydrogen is flowed in reaction vessel,, reaction vessel was heated 5 minutes with 80 ℃ further with behind the 13Pa that reduces pressure in the system with 100mL/ minute flow.From ship type container, produce mist, observe stores being provided with on the nigh quartz base plate.After mist produces and accomplishes; Stop decompression, with recovering pressure in the nitrogen adding system, then; Flow with 200mL/ minute under 101.3kPa makes the nitrogen (content of hydrogen: 3 volume %) flow; The temperature of reaction vessel is elevated to 350 ℃, directly kept 1 hour, the result obtains to have the film of metalluster on substrate.The thickness of this film is 0.05 μ m.
Measure the ESCA spectrum of this film, the result observes at 280eV and 284eV and belongs to Ru
3dThe metal Ru of not observing fully from the peak of other element can be known in the peak of track.In addition, for this ruthenium film, the result who adopts 4 terminal method evaluations than resistance is shown in table 1.
For ruthenium film in this formation, adopt the adaptation of checker test evaluation and substrate, the result does not observe substrate fully and the ruthenium film is peeled off.
(2) storage stability test
As the affirmation of storage stability, carry out research for the deterioration of heat.Five (trifluoro phosphine) ruthenium (0) 1g are added in the withstand voltage encloses container of stainless steel of 100mL capacity, airtight under nitrogen atmosphere, behind the 13Pa that in system, reduces pressure integral container is heated to 80 ℃ of keepings.After 1 month, there is not the apparent variation of five (trifluoro phosphine) rutheniums (0) yet.
Afterwards, container is returned to room temperature, after in the dry nitrogen displacement container, utilize the main points identical with above-mentioned (1) to implement film forming, the result obtains to have the film of metalluster on substrate.For the various rerum naturas of the metal Ru film that obtains, likewise estimate with above-mentioned (1).The result is shown in table 1.
(3) gasification property test
As the affirmation of gasification property, adopt following TP to carry out the mensuration of amount of vaporization.Be accommodated in the withstand voltage stainless steel container made of band valve of 100mL capacity five (trifluoro phosphine) ruthenium (0) 1g and sealing in the glove box under dry nitrogen atmosphere room temperature.Afterwards, container is placed on the hot plate, open valve, reduced pressure treatment carried out 5 minute in to container 80 ℃ of following heating edge in the limit under 13Pa.Behind the valve-off, placement was cooled off 3 hours and container is returned to room temperature afterwards, in above-mentioned glove box, opens valve lentamente the pressure recovery in the container is arrived normal pressure.Open container measurement residual sample amount afterwards, the amount of vaporization when calculating reduced pressure treatment thus, amount of vaporization is 0.85g as a result.
In addition, utilize the main points identical with embodiment 1 (2) to carry out similarly for the gasification property of having preserved 1 month five (trifluoro phosphine) ruthenium (0) 1g, thereby calculate amount of vaporization, amount of vaporization is 0.84g as a result.The result is shown in table 1.
[ embodiment 2 ]
(1) formation of ruthenium film
Adopt five (triethyl phosphine) ruthenium (0) 0.05g that obtains in the synthetic example 2 to replace five (trifluoro phosphine) ruthenium (0) 0.05g, in addition, likewise carry out, thereby on substrate, obtain to have the film of metalluster with embodiment 1.Various rerum naturas and embodiment 1 for the metal Ru film that obtains estimate equally.The result is shown in table 1.
(2) storage stability test
As the affirmation of storage stability, adopt five (triethyl phosphine) ruthenium (0) 1g that obtains in the synthetic example 2 to replace five (trifluoro phosphine) ruthenium (0) 1g, in addition, likewise estimate with embodiment 1.The result is shown in table 1.
(3) gasification property test
As the affirmation of gasification property, adopt five (triethyl phosphine) ruthenium (0) 1g that obtains in the synthetic example 2 to replace five (trifluoro phosphine) ruthenium (0) 1g, in addition, likewise implement the mensuration of amount of vaporization with embodiment 1.The result is shown in table 1.
[ embodiment 3 ]
(1) formation of ruthenium film
Adopt (1, the 5-cyclooctadiene) three (trifluoro phosphine) ruthenium (0) 0.05g that obtain in the synthetic example 3 to replace five (trifluoro phosphine) ruthenium (0) 0.05g, in addition, likewise carry out, thereby on substrate, obtain to have the film of metalluster with embodiment 1.Various rerum naturas and embodiment 1 for the metal Ru film that obtains estimate equally.The result is shown in table 1.
(2) storage stability test
As the affirmation of storage stability, adopt (1, the 5-cyclooctadiene) three (trifluoro phosphine) ruthenium (0) 1g that obtain in the synthetic example 3 to replace five (trifluoro phosphine) ruthenium (0) 1g, in addition, likewise estimate with embodiment 1.The result is shown in table 1.
(3) gasification property test
As the affirmation of gasification property, adopt (1, the 5-cyclooctadiene) three (trifluoro phosphine) ruthenium (0) 1g that obtain in the synthetic example 3 to replace five (trifluoro phosphine) ruthenium (0) 1g, in addition, likewise implement the mensuration of amount of vaporization with embodiment 1.The result is shown in table 1.
[ embodiment 4 ]
(1) formation of ruthenium film
Adopt (1, the 5-cyclooctadiene) three (trimethyl-phosphine) ruthenium (0) 0.05g that obtains in the synthetic example 4 to replace five (trifluoro phosphine) ruthenium (0) 0.05g, in addition, likewise carry out, thereby on substrate, obtain to have the film of metalluster with embodiment 1.Various rerum naturas and embodiment 1 for the metal Ru film that obtains estimate equally.The result is shown in table 1.
(2) storage stability test
As the affirmation of storage stability, adopt (1, the 5-cyclooctadiene) three (trimethyl-phosphine) ruthenium (0) 1g that obtains in the synthetic example 4 to replace five (trifluoro phosphine) ruthenium (0) 1g, in addition, likewise estimate with embodiment 1.The result is shown in table 1.
(3) gasification property test
As the affirmation of gasification property, adopt (1, the 5-cyclooctadiene) three (trimethyl-phosphine) ruthenium (0) 1g that obtains in the synthetic example 4 to replace five (trifluoro phosphine) ruthenium (0) 1g, in addition, likewise implement the mensuration of amount of vaporization with embodiment 1.The result is shown in table 1.
[ embodiment 5 ]
(1) formation of ruthenium film
Adopt four (trifluoro phosphine) dihydro ruthenium (II) 0.05g that obtain in the synthetic example 5, making reaction vessel be-50 ℃, to replace five (trifluoro phosphine) ruthenium (0) 0.05g, make reaction vessel be 80 ℃; In addition; Likewise carry out with embodiment 1, thereby on substrate, obtain to have the film of metalluster.Various rerum naturas and embodiment 1 for the metal Ru film that obtains estimate equally.The result is shown in table 1.
(2) storage stability test
As the affirmation of storage stability, implement deterioration research.Four (trifluoro phosphine) dihydro ruthenium (II) 1g are packed in the withstand voltage encloses container of stainless steel of 100mL capacity and airtight under nitrogen atmosphere, behind the 13Pa that in system, reduces pressure integral container is cooled to-50 ℃ of keepings.After 1, there is not the apparent variation of four (trifluoro phosphine) dihydro rutheniums (II) yet.
Afterwards, container is returned to room temperature, after in the dry nitrogen displacement container, utilize the main points identical with above-mentioned (1) to implement film forming, the result obtains to have the film of metalluster on substrate.For the various rerum naturas of the metal Ru film that obtains, likewise estimate with above-mentioned (1).The result does not observe variation.The result is shown in table 1.
(3) gasification property test
As the affirmation of gasification property, adopt following TP to carry out the mensuration of amount of vaporization.Be accommodated in the withstand voltage stainless steel container made of band valve of 100mL capacity four (trifluoro phosphine) dihydro ruthenium (II) 1g and sealing in the glove box under dry nitrogen atmosphere room temperature.Afterwards, container is placed on the hot plate, open valve, the limit-50 ℃ down the cooling limits under 13Pa, carried out reduced pressure treatment 5 minutes in to container.Behind the valve-off, container is returned to room temperature afterwards, in above-mentioned glove box, open valve lentamente the pressure recovery in the container is arrived normal pressure through 3 hours.Open container measurement residual sample amount afterwards, the amount of vaporization when calculating reduced pressure treatment thus, amount of vaporization is 0.98g as a result.
In addition, utilize and carry out similarly for the gasification property of having preserved 1 month four (trifluoro phosphine) dihydro ruthenium (II) 1g with embodiment 5 (2) identical main points, thereby calculate amount of vaporization, amount of vaporization is 1.00g as a result.The result is shown in table 1.
[ embodiment 6 ]
(1) formation of ruthenium film
Adopt (1, the 5-octadiene) three (trifluoro phosphine) ruthenium (0) 0.05g that obtain in the synthetic example 6 to replace five (trifluoro phosphine) ruthenium (0) 0.05g, in addition, likewise carry out, thereby on substrate, obtain to have the film of metalluster with embodiment 1.Various rerum naturas and embodiment 1 for the metal Ru film that obtains estimate equally.The result is shown in table 1.
(2) storage stability test
As the affirmation of storage stability, adopt (1, the 5-octadiene) three (trifluoro phosphine) ruthenium (0) 1g that obtain in the synthetic example 6 to replace five (trifluoro phosphine) ruthenium (0) 1g, in addition, likewise estimate with embodiment 1.The result is shown in table 1.
(3) gasification property test
As the affirmation of gasification property, adopt (1, the 5-octadiene) three (trifluoro phosphine) ruthenium (0) 1g that obtain in the synthetic example 6 to replace five (trifluoro phosphine) ruthenium (0) 1g, in addition, likewise implement the mensuration of amount of vaporization with embodiment 1.The result is shown in table 1.
[ embodiment 7 ]
(1) formation of ruthenium film
Adopt (dichloro) four (trifluoro phosphine) ruthenium (II) 0.05g that obtains in the synthetic example 7 to replace four (trifluoro phosphine) dihydro ruthenium (II) 0.05g, in addition, likewise carry out, thereby on substrate, obtain to have the film of metalluster with embodiment 5.Various rerum naturas and embodiment 5 for the metal Ru film that obtains estimate equally.The result is shown in table 1.
(2) storage stability test
As the affirmation of storage stability, adopt (dichloro) four (trifluoro phosphine) ruthenium (II) 1g that obtains in the synthetic example 7 to replace four (trifluoro phosphine) dihydro ruthenium (II) 1g, in addition, likewise estimate with embodiment 5.The result is shown in table 1.
(3) gasification property test
As the affirmation of gasification property, adopt (dichloro) four (trifluoro phosphine) ruthenium (II) 1g that obtains in the synthetic example 7 to replace four (trifluoro phosphine) dihydro ruthenium (II) 1g, in addition, likewise implement the mensuration of amount of vaporization with embodiment 5.The result is shown in table 1.
[table 1]
Claims (6)
1. material is used in a ruthenium film formation that contains the compound of following formula (1) expression,
Ru(PR
1 3)
l(L
1)
m(L
2)
n (1)
In the said formula (1), R
1Independently of one another for Wasserstoffatoms, halogen atom, carbonatoms are that 1~4 alkyl or carbonatoms are 1~4 halo alkyl, L
1Be Wasserstoffatoms or halogen atom, L
2Be that carbonatoms with at least two two keys is 4~10 unsaturated hydrocarbon compound, l is 1~5 integer, and m is 0~4 integer, and n is 0~2 integer, wherein, and l+m+2n=5 or 6.
2. ruthenium film according to claim 1 forms and uses material, is used for the chemical vapor-phase growing method.
3. a ruthenium film formation method wherein, is used claim 1 or 2 described ruthenium films to form and is used material.
4. a ruthenium film formation method comprises that the described ruthenium film of claim 2 is formed the ruthenium film formation that supplies on the matrix with material to be supplied with operation and this ruthenium film formation is formed operation with the film that the material thermal degradation is formed on the said matrix ruthenium film with material.
5. ruthenium film formation method according to claim 4, wherein, the temperature that said film forms the thermal degradation in the operation is 100 ℃~800 ℃.
6. according to claim 4 or 5 described ruthenium film formation methods, wherein, the thermal degradation that said film forms in the operation is carried out in non-active gas or reducing gas.
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