US20060024443A1 - Chemical vapor deposition material and chemical vapor deposition - Google Patents
Chemical vapor deposition material and chemical vapor deposition Download PDFInfo
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- US20060024443A1 US20060024443A1 US11/187,982 US18798205A US2006024443A1 US 20060024443 A1 US20060024443 A1 US 20060024443A1 US 18798205 A US18798205 A US 18798205A US 2006024443 A1 US2006024443 A1 US 2006024443A1
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- ruthenium
- film
- vapor deposition
- chemical vapor
- carbon atoms
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- 238000005229 chemical vapour deposition Methods 0.000 title claims abstract description 38
- 239000000463 material Substances 0.000 title claims abstract description 36
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 77
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 54
- 238000000034 method Methods 0.000 claims abstract description 27
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 24
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract description 17
- 239000003446 ligand Substances 0.000 claims abstract description 13
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 11
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 4
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 4
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims abstract description 4
- -1 hydrogen anion Chemical group 0.000 claims description 50
- 239000001257 hydrogen Substances 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 150000003304 ruthenium compounds Chemical class 0.000 abstract description 6
- 239000010408 film Substances 0.000 description 79
- 229910052757 nitrogen Inorganic materials 0.000 description 68
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 54
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 43
- 239000000243 solution Substances 0.000 description 24
- 239000000758 substrate Substances 0.000 description 22
- 239000007789 gas Substances 0.000 description 16
- 239000007983 Tris buffer Substances 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 15
- 239000002184 metal Substances 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- 239000010453 quartz Substances 0.000 description 13
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- 238000013019 agitation Methods 0.000 description 12
- 150000003303 ruthenium Chemical class 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 11
- DHCWLIOIJZJFJE-UHFFFAOYSA-L dichlororuthenium Chemical compound Cl[Ru]Cl DHCWLIOIJZJFJE-UHFFFAOYSA-L 0.000 description 10
- 239000010410 layer Substances 0.000 description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 0 [1*]NC([2*])N[3*] Chemical compound [1*]NC([2*])N[3*] 0.000 description 8
- 239000003990 capacitor Substances 0.000 description 8
- SYCZCVFOEPCWBF-UHFFFAOYSA-N n,n'-di(propan-2-yl)ethanimidamide Chemical compound CC(C)NC(C)=NC(C)C SYCZCVFOEPCWBF-UHFFFAOYSA-N 0.000 description 8
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 7
- 229910001873 dinitrogen Inorganic materials 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 229910003002 lithium salt Inorganic materials 0.000 description 6
- 159000000002 lithium salts Chemical class 0.000 description 6
- 239000003595 mist Substances 0.000 description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- 239000003989 dielectric material Substances 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 239000012212 insulator Substances 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- ZUHLLHJBEFJMKQ-UHFFFAOYSA-N n,n'-ditert-butylethanimidamide Chemical compound CC(C)(C)NC(C)=NC(C)(C)C ZUHLLHJBEFJMKQ-UHFFFAOYSA-N 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- PPAXFJNSJJMILV-UHFFFAOYSA-N ruthenium dihydride Chemical compound [RuH2] PPAXFJNSJJMILV-UHFFFAOYSA-N 0.000 description 4
- JDNQPKBFOBQRBN-UHFFFAOYSA-N ruthenium monohydride Chemical compound [RuH] JDNQPKBFOBQRBN-UHFFFAOYSA-N 0.000 description 4
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 4
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010908 decantation Methods 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 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 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000001312 dry etching Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- LGRLWUINFJPLSH-UHFFFAOYSA-N methanide Chemical compound [CH3-] LGRLWUINFJPLSH-UHFFFAOYSA-N 0.000 description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229910052454 barium strontium titanate Inorganic materials 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011229 interlayer Substances 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
- 229910052451 lead zirconate titanate Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 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
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000001272 nitrous oxide Substances 0.000 description 1
- 238000009304 pastoral farming Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 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 1
- 239000000523 sample Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- 230000008016 vaporization Effects 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
- C07F15/0046—Ruthenium compounds
- C07F15/0053—Ruthenium compounds without a metal-carbon linkage
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
-
- 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
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
Abstract
A chemical vapor deposition material comprising a ruthenium compound having a ligand represented by the following formula:
wherein R1, R2 and R3 are each independently a hydrogen atom, fluorine atom, trifluoromethyl group or hydrocarbon group having 1 to 10 carbon atoms, and a method of forming a ruthenium film from the chemical vapor deposition material by chemical vapor deposition. A high-quality ruthenium film even when it is very thin can be obtained.
wherein R1, R2 and R3 are each independently a hydrogen atom, fluorine atom, trifluoromethyl group or hydrocarbon group having 1 to 10 carbon atoms, and a method of forming a ruthenium film from the chemical vapor deposition material by chemical vapor deposition. A high-quality ruthenium film even when it is very thin can be obtained.
Description
- The present invention relates to a chemical vapor deposition material and chemical vapor deposition.
- It is becoming difficult to ensure the capacity of a memory cell with the prior art to meet drastic demand for higher integration and a finer pattern rule for semiconductor devices typified by DRAM (Dynamic Random Access Memory). To cope with this, the alteration of the materials of metal films and metal oxide films constituting these devices is becoming necessary to obtain a finer pattern rule.
- Particularly, the improvement of a conductive metal film for use in the multi-layer wiring of a semiconductor device is desired. Although aluminum has been used as a wiring material, it is being replaced by copper having a resistivity 60% lower than that of aluminum. In order to improve the conductivity of this copper wiring, a low-dielectric material (Low-k material) is used as an interlayer dielectric material for this multi-layer wiring. However, an oxygen atom contained in this Low-k material is taken into the copper wiring easily to reduce its conductivity. Therefore, studies are being made on technology for forming a barrier film between the Low-k material and the copper wiring in order to prevent the movement of oxygen from the Low-k material. As the material of this barrier film, studies are being made on use of platinum and ruthenium as an insulator, all of which hardly take in oxygen from the dielectric layer and use of ruthenium oxide which has conductivity. It is known that, out of these, a platinum film is hardly processed by dry etching whereas a metal ruthenium film or ruthenium oxide film can be relatively easily processed by dry etching and can be suitably used as a barrier film material.
- As dielectric materials for capacitor insulators for which a laminated film (ON film) consisting of silicon oxide and silicon nitride layers has been used, materials having a perovskite crystal structure and an extremely large dielectric constant than the ON film, such as barium titanate, strontium titanate and PZT, have been studied to achieve higher integration and a finer pattern rule. However, even when these high-dielectric materials are used as a capacitor insulator, a low dielectric layer may be formed at the interface between an electrode and a dielectric, thereby forming an obstacle to the improvement of capacitance. It is considered that this low-dielectric layer is formed by the movement of an oxygen atom from the dielectric layer to the electrode material. Then, platinum, ruthenium and ruthenium oxide are studied as electrode materials which hardly take in oxygen from the dielectric layer. It is known that a metal ruthenium film or ruthenium oxide film can be suitably used as an electrode for a capacitor having a perovskite structure dielectric as an insulator because it can be easily processed as described above (Nikkei Micro-device, pp. 93-106, February 2000, Electronic Materials, pp. 47-49, November 2003, Jpn. J. Appl. Phys., Vol. 43, No. 6A, pp. 3315-3319, 2004).
- Although sputtering has been employed for the formation of the above metal ruthenium film, chemical vapor deposition is now under study to obtain a fine structure, reduce the film thickness and realize mass-production (JP-A 11-340435, JP-A 2002-161367, JP-A 2002-212112, JP-A 2002-523634 and JP-A 2002-69639) (the term “JP-A” as used herein means an “unexamined published Japanese patent application”).
- However, in general, a metal film formed by chemical vapor deposition has poor surface morphology as the assembly state of the fine crystals of the film is sparse. When this metal film is used as a capacitor electrode, an increase in leak current caused by the concentration of a field occurs. When a very thin electrode is to be formed so as to realize a fine pattern rule, a film having a defect that metal portions are scattered like islands and not a uniform film is obtained with the result of reduced electric conductivity. When this film is used as a capacitor electrode, a large capacitor area cannot be obtained and capacitance required for the operation of the capacitor cannot be ensured.
- In order to solve the above morphology problem, studies are being made on use of bis(dipivaloylmethanato)ruthenium or ruthenocene.bis(alkylcyclopentadienyl)ruthenium as a chemical vapor deposition material (refer to JP-A 06-283438, JP-A 11-35589 and JP-A 2002-114795).
- However, in the method making use of these chemical vapor deposition materials, morphology and the step coverage of a 3-D substrate are improved but the obtained film is inferior to a ruthenium film formed by sputtering in conductivity and the formed ruthenium film contains impurities in large quantities. Therefore, when a ruthenium film formed from any one of these raw materials by chemical vapor deposition is used as an electrode for DRAM, the performance of the DRAM becomes unsatisfactory.
- Further, technology making use of these chemical vapor deposition materials has a problem that it is difficult to form a super thin film required for the reduction of the pattern rule (particularly, 10 nm or less) and therefore cannot realize a DRAM having a fine pattern. To realize the formation of a super thin film, monatomic layer deposition is studied and a technique for forming a metal cobalt metal copper film by the monatomic layer deposition is reported (refer to JP-A 2002-367992 and Nature Materials, Vol. 2, pp. 749-754, November 2003).
- However, this method has a problem with production yield due to its complicated process.
- It is an object of the present invention which has been made in view of the above problem to provide a chemical vapor deposition material which can provide a high-quality ruthenium film even when it is very thin and a simple method of forming a ruthenium film from the chemical vapor deposition material.
- According to the present invention, firstly, the above object can be attained by a chemical vapor deposition material represented by the following formula (1):
Ru3+LnXmYl (1)
wherein L is a ligand represented by the following formula (2):
wherein R1, R2 and R3 are each independently a hydrogen atom, fluorine atom, trifluoromethyl group or hydrocarbon group having 1 to 10 carbon atoms, - X is a hydrogen anion, halogen anion, monovalent hydrocarbon anion having 1 to 10 carbon atoms or ligand represented by the following formula (3):
wherein R4, R5, R6, R7 and R8 are each independently a hydrogen atom, hydrocarbon group having 1 to 10 carbon atoms or trimethylsilyl group, with the proviso that when at least two out of R4, R5 , R6, R7 and R8 are hydrocarbon groups having 1 to 10 carbon atoms, they may be bonded together to form a 4- to 8-membered ring, - Y is a ligand represented by the following formula (4):
wherein R9, R10, R11, R12, R13 and R14 are each independently a hydrogen atom or hydrocarbon group having 1 to 10 carbon atoms, - n is an integer of 1 to 3, m is an integer of 0 to 2, 1 is 0 or 1, and (n+m) is 3.
- According to the present invention, secondly, the above object of the present invention is attained by a method of forming a ruthenium film from the above chemical vapor deposition material by chemical vapor deposition.
- Detailed description of the present invention are followed hereinafter.
- The chemical vapor deposition material of the present invention is represented by the above formula (1).
- In the above formula (1), L is represented by the above formula (2).
- In the above formula (2), R1, R2 and R3 are each independently a hydrogen atom, fluorine atom, trifluoromethyl group or hydrocarbon group having 1 to 10 carbon atoms. The hydrocarbon group having 1 to 10 carbon atoms is preferably a hydrocarbon group having 1 to 6 carbon atoms, as exemplified by methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, neopentyl group, n-hexyl group and cyclohexyl group. As for preferred examples of R1, R2 and R3, R1 and R3 are each preferably an isopropyl group, t-butyl group, neopentyl group or cyclohexyl group, and R2 is preferably a hydrogen atom, methyl group, ethyl group or t-butyl group.
- In the above formula (1), X is a hydrogen anion, halogen anion, monovalent hydrocarbon anion having 1 to 10 carbon atoms or ligand represented by the above formula (3).
- In the above formula (3), R4, R5, R6, R7 and R8 are each independently a hydrogen atom, hydrocarbon group having 1 to 10 carbon atoms or trimethylsilyl group. When at least two out of R4, R5, R6, R7 and R8 are hydrocarbon groups having 1 to 10 carbon atoms, they may be bonded together to form a 4- to 8-membered ring. Examples of the hydrocarbon group having 1 to 10 carbon atoms include methyl group and ethyl group. As an example where they are bonded together to form a ring, two adjacent carbon atoms out of carbon atoms forming a 5-membered ring of the above formula (3) are bonded to carbon atoms at the first-position and fourth-position of a group —CH2CH2CH2CH2— to form a six-membered ring.
- In the above formula (4), R9, R10, R11, R12, R13 and R14 are each independently a hydrogen atom or hydrocarbon group having 1 to 10 carbon atoms. The hydrocarbon group having 1 to 10 carbon atoms is preferably an alkyl group having 1 to 4 carbon atoms, as exemplified by methyl group and ethyl group.
- X in the above formula (1) is preferably a hydrogen anion, chlorine anion, methyl anion, ethyl anion, η5-cyclopentadienyl group, η5-tetramethylcyclopentadienyl group, η5-trimethylsilylcyclopentadienyl group, η5-indenyl group, η6-benzene or η6-toluene, more preferably a hydrogen anion, methyl anion or η5-cyclopentadienyl group.
- In the above formula (1), n is an integer of 1 to 3, m is an integer of 0 to 2, l is 0 or 1, and (n+m) is 3.
- Illustrative examples of the chemical vapor deposition material represented by the above formula (1) include tris(η3-N,N′-diisopropylacetamidinate)ruthenium, bis(η3-N,N′-diisopropylacetamidinate)ruthenium chloride, (η3-N,N′-diisopropylacetamidinate)ruthenium dichloride, tris(η3-N,N′-di-t-butylacetamidinate)ruthenium, bis(η3-N,N′-di-t-butylacetamidinate)ruthenium chloride, (η3-N,N′-di-t-butylacetamidinate(ruthenium dichloride, tris(η3-N,N′-dicyclohexylacetamidinate)ruthenium, bis(η3-N,N′-dicyclohexylacetamidinate)ruthenium chloride, (η3-N,N′-dicyclohexylacetamidinate)ruthenium dichloride, tris(η3-N-t-butyl-N′-ethylacetamidinate)ruthenium, bis(η3-N-t-butyl-N′-ethylacetamidinate)ruthenium chloride, (η3-N-t-butyl-N′-ethylacetamidinate)ruthenium dichloride, bis(η3-N,N′-diisopropylacetamidinate)ruthenium hydride, (η3-N,N′-diisopropylacetamidinate)ruthenium dihydride, bis(η3-N,N′-di-t-butylacetamidinate)ruthenium hydride, (η3-N,N′-di-t-butylacetamidinate)ruthenium dihydride, bis(η3-N,N′-dicyclohexylacetamidinate)ruthenium hydride, (η3-N,N′-dicyclohexylacetamidinate)ruthenium dihydride, bis(η3-N-t-butyl-N′-ethylacetamidinate)ruthenium hydride, (η3-N-t-butyl-N′-ethylacetamidinate)ruthenium dihydride, bis(η3-N,N′-diisopropylacetamidinate)methyl ruthenium, (η3-N,N′-diisopropylacetamidinate)dimethyl ruthenium, bis(η3-N,N′-di-t-butylacetamidinate)methyl ruthenium, (η3-N,N′-di-t-butylacetamidinate)dimethyl ruthenium, bis(η3-N,N′-dicyclohexylacetamidinate)methyl ruthenium, (η3-N,N′-dicyclohexylacetamidinate)dimethyl ruthenium, bis(η3-N-t-butyl-N′-ethylacetamidinate)methyl ruthenium, (η3-N-t-butyl-N′-ethylacetamidinate)dimethyl ruthenium, bis(η3-N,N′-diisopropylacetamidinate)(η5-cyclopentadienyl)ruthenium, (η3-N,N′-diisopropylacetamidinate)di(η5-cyclopentadienyl)ruthenium, bis(η3-N,N′-di-t-butylacetamidinate)(η5-cyclopentadienyl)ruthenium, (η3-N,N′-di-t-butylacetamidinate)di(η5-cyclopentadienyl)ruthenium, bis(η3-N,N′-dicyclohexylacetamidinate)(η5-cyclopentadienyl)ruthenium, (η3-N,N′-dicyclohexylacetamidinate)di(η5-cyclopentadienyl)ruthenium, bis(η3-N-t-butyl-N′-ethylacetamidinate) (η5-cyclopentadienyl)ruthenium and (η3-N-t-butyl-N′-ethylacetamidinate)di(η5-cyclopentadienyl)ruthenium.
- Out of these, preferred are tris(η3-N,N′-diisopropylacetamidinate)ruthenium, bis(η3-N,N′-diisopropylacetamidinate)ruthenium chloride, (η3-N,N′-diisopropylacetamidinate)ruthenium dichloride, tris(η3-N,N′-di-t-butylacetamidinate)ruthenium, bis(η3-N,N′-di-t-butylacetamidinate)ruthenium chloride, (η3-N,N′-di-t-butylacetamidinate)ruthenium dichloride, tris(η3-N,N′-dicyclohexylacetamidinate)ruthenium, bis(η3-N,N′-dicyclohexylacetamidinate)ruthenium chloride and (η3-N,N′-dicyclohexylacetamidinate)ruthenium dichloride.
- These compounds as a chemical vapor deposition material may be used alone or in combination of two or more. Preferably, they are used alone.
- The above ruthenium compound can be synthesized by the general method of synthesizing a metal complex in accordance with the method disclosed in Inorg. Chem., 44(6), pp. 1728-1735 (2005). For example, it can be synthesized by reacting ruthenium halide with an alkali metal salt of a desired ligand in the presence of a suitable solvent. To synthesize a ruthenium compound having different ligands, ruthenium halide is reacted with a predetermined amount of an alkali metal salt of one ligand and then with a predetermined amount of an alkali metal salt of another ligand.
- The halogen atom contained in the above ruthenium halide is preferably a chlorine atom or bromine atom, and the alkali metal contained in the alkali metal salt of the ligand is preferably lithium, sodium or potassium.
- The above chemical vapor deposition material is used in the chemical vapor deposition of the present invention.
- The chemical vapor deposition of the present invention may be a process known per se except that the above chemical vapor deposition material is used. For instance, it can be carried out as follows.
- (1) The chemical vapor deposition material of the present invention is vaporized, and then (2) the resulting vapor is thermally decomposed by heating to deposit ruthenium on a substrate. Even when the above step (1) is accompanied by the decomposition of the chemical vapor deposition material of the present invention, the effect of the present invention is not lessened.
- The substrate which can be used herein is made of a suitable material such as glass, silicon semiconductor, quartz, metal, metal oxide or synthetic resin. It is preferably a material which can stand the temperature of the step of thermally decomposing the ruthenium compound.
- In the above step (1), the temperature for vaporizing the ruthenium compound is preferably 50 to 350° C., more preferably 80 to 300° C.
- In the above step (2), the temperature for thermally decomposing the ruthenium compound is preferably 80 to 500° C., more preferably 100 to 400° C., most preferably 120 to 350° C.
- The chemical vapor deposition of the present invention may be carried out in the presence or absence of an inert gas or the presence or absence of a reduction gas. Alternatively, it may be carried out in the presence of both the inert gas and the reduction gas. Examples of the inert gas include nitrogen, argon and helium. Examples of the reduction gas include hydrogen and ammonia. When the chemical vapor deposition material represented by the above formula (1) contains elemental halogen, the chemical vapor deposition is preferably carried out in the presence of a reduction gas.
- The chemical vapor deposition of the present invention can be carried out in the coexistence of an oxidizing gas. Examples of the oxidizing gas include oxygen and nitrous oxide. When the oxidizing gas is coexistent, the amount of the oxidizing gas in the atmosphere is preferably 1 to 70 mol %, more preferably 3 to 40 mol %.
- The chemical vapor deposition of the present invention can be carried out under increased pressure, normal pressure or reduced pressure. It is preferably carried out under normal pressure or reduced pressure, more preferably under a pressure of 15,000 Pa or less.
- The ruthenium film thus obtained has high purity and high electric conductivity as obvious from Examples which are given hereinafter. A super thin ruthenium film having a thickness of 10 nm or less can be formed from the chemical vapor deposition material of the present invention and can be advantageously used as a barrier film for wiring electrodes and a capacitor electrode.
- As described above, according to the present invention, there are provided a chemical vapor deposition material which can provide a high-quality ruthenium film even when it is very thin and a simple method of forming a ruthenium film from the chemical vapor deposition material.
- The following examples are provided to further illustrate the present invention.
- 5.7 g of N,N′-diisopropylacetamidine was weighed and placed in a 200 ml flask whose inside had been substituted by nitrogen and left at 50° C. under reduced pressure for 60 minutes. After the inside temperature of the flask was returned to room temperature, the flask was filled with dry nitrogen. 50 ml of well dried diethyl ether was added to the flask in a nitrogen atmosphere and stirred to dissolve the above N,N′-diisopropylacetamidine. This solution was cooled to −60° C., and 22 ml of a diethyl ether solution of butyl lithium (concentration of 2.0 mol/l) was added dropwise under agitation over 30 minutes and further stirred for another 3 hours. Agitation was stopped, the inside temperature of the flask was returned to room temperature over 2 hours, and the supernatant was collected with a syringe to obtain a diethyl ether solution of a lithium salt of N,N′-diisopropylacetamidine.
- Meanwhile, 2.1 g of anhydrous ruthenium trichloride was weighed and placed in a 200 ml flask whose inside had been substituted by nitrogen and left at 50° C. under reduced pressure for 60 minutes. After the inside temperature of the flask was returned to room temperature, the flask was filled with dry nitrogen. 50 ml of well dried diethyl ether and 50 ml of well dried tetrahydrofuran were added to the flask in a nitrogen atmosphere to dissolve the above anhydrous ruthenium trichloride. This solution was cooled to −60° C., and the above prepared diethyl ether solution of a lithium salt of N,N′-diisopropylacetamidine was added dropwise under agitation over 60 minutes and further stirred at the same temperature for another 5 hours. Agitation was stopped, the inside temperature of the flask was returned to room temperature over 2 hours, and the solution was left for another 1 hour. After the formed precipitate was removed by decantation, part of the solvent was removed under reduced pressure, and the resulting solution was concentrated. The thus obtained viscous solution was subjected to column chromatography by using a mixed solvent of diethyl ether and tetrahydrofuran (mixing ratio of 1/1 (volume ratio)) and a neutral alumina column to collect a red brown portion. After concentration under reduced pressure, the solvent was removed by heating at 40° C. and 133 Pa for 2 hours to obtain 0.9 g of tris (η3-N,N′-diisopropylacetamidinate)ruthenium as a red purple solid. The yield rate was 17%.
- When the elemental analysis of the obtained solid was carried out, it contained 55.7% of carbon, 8.21% of hydrogen and 17.2% of nitrogen. As for the theoretical values of tris(η3-N,N′-diisopropylacetamidinate)ruthenium, it contains 54.9% of carbon, 9.80% of hydrogen and 16.0% of nitrogen.
- 2.1 g of N,N′-diisopropylacetamidine was weighed and placed in a 100 ml flask whose inside had been substituted by nitrogen and left at 50° C. under reduced pressure for 60 minutes. After the inside temperature of the flask was returned to room temperature, the flask was filled with dry nitrogen. 20 ml of well dried diethyl ether was added to the flask in a nitrogen atmosphere and stirred to dissolve the above N,N′-diisopropylacetamidine. This solution was cooled to −60° C., and 9 ml of a diethyl ether solution of butyl lithium (concentration of 2.0 mol/l) was added dropwise under agitation over 30 minutes and further stirred for another 3 hours. Agitation was stopped, the inside temperature of the flask was returned to room temperature over 2 hours, and the supernatant was collected with a syringe to obtain a diethyl ether solution of a lithium salt of N,N′-diisopropylacetamidine.
- Meanwhile, 2.1 g of anhydrous ruthenium trichloride was weighed and placed in a 200 ml flask whose inside had been substituted by nitrogen and left at 50° C. under reduced pressure for 60 minutes. After the inside temperature of the flask was returned to room temperature, the flask was filled with dry nitrogen. 50 ml of well dried diethyl ether and 50 ml of well dried tetrahydrofuran were added to the flask to dissolve the above anhydrous ruthenium trichloride. This solution was cooled to −60° C., and the above prepared diethyl ether solution of a lithium salt of N,N′-diisopropylacetamidine was added dropwise under agitation over 60 minutes and further stirred for another 5 hours. Agitation was stopped, the inside temperature of the flask was returned to room temperature over 2 hours, and the solution was left for another 1 hour. After the formed precipitate was removed by decantation, part of the solvent was removed under reduced pressure, and the resulting solution was concentrated. The thus obtained viscous solution was subjected to column chromatography by using a mixed solvent of diethyl ether and tetrahydrofuran (mixing ratio of 1/1 (volume ratio)) and a neutral alumina column to collect a red brown portion. After concentration under reduced pressure, the solvent was removed by heating at 40° C. and 133 Pa for 2 hours to obtain 1.3 g of (η3-N,N′-diisopropylacetamidinate)ruthenium dichloride as a dark brown solid. The yield rate was 41%.
- When the elemental analysis of the obtained solid was carried out, it contained 32.4% of carbon, 5.08% of hydrogen and 9.11% of nitrogen. As for the theoretical values of (η3-N,N′-diisopropylacetamidinate)ruthenium dichloride, it contains 30.7% of carbon, 5.47% of hydrogen and 8.94% of nitrogen.
- 6.8 g of N,N′-di-t-butylacetamidine was weighed and placed in a 200 ml flask whose inside had been substituted by nitrogen and left at 50° C. under reduced pressure for 60 minutes. After the inside temperature of the flask was returned to room temperature, the flask was filled with dry nitrogen. 50 ml of well dried diethyl ether was added to the flask in a nitrogen atmosphere and stirred to dissolve the above N,N′-di-t-butylacetamidine. This solution was cooled to −60° C., 22 ml of a diethyl ether solution of butyl lithium (concentration of 2.0 mol/l) was added dropwise under agitation over 30 minutes and further stirred for another 3 hours. Agitation was stopped, the inside temperature of the flask was returned to room temperature over 2 hours, and the supernatant was collected with a syringe to obtain a diethyl ether solution of a lithium salt of N,N′-di-t-butylacetamidine.
- Meanwhile, 2.1 g of anhydrous ruthenium trichloride was weighed and placed in a 200 ml flask whose inside had been substituted by nitrogen and left at 50° C. under reduced pressure for 60 minutes. After the inside temperature of the flask was returned to room temperature, the flask was filled with dry nitrogen. 50 ml of well dried diethyl ether and 50 ml of well dried tetrahydrofuran were added to the flask to dissolve the above anhydrous ruthenium trichloride. This solution was cooled to −60° C., and the above prepared diethyl ether solution of a lithium salt of N,N′-di-t-butylacetamidine was added dropwise under agitation over 60 minutes and further stirred for another 5 hours. Agitation was stopped, the inside temperature of the flask was returned to room temperature over 2 hours, and the solution was left for another 1 hour. After the formed precipitate was removed by decantation, part of the solvent was removed under reduced pressure, and the resulting solution was concentrated. The thus obtained viscous solution was subjected to column chromatography by using a mixed solvent of diethyl ether and tetrahydrofuran (mixing ratio of 1/1 (volume ratio)) and a neutral alumina column to collect a red brown portion. After concentration under reduced pressure, the solvent was removed by heating at 40° C. and 133 Pa for 2 hours to obtain 1.2 g of tris(η3-N,N′-di-t-butylacetamidinate)ruthenium as a red purple solid. The yield rate was 19%.
- When the elemental analysis of the obtained solid was carried out, it contained 60.9% of carbon, 9.94% of hydrogen and 13.0% of nitrogen. As for the theoretical values of tris(η3-N,N′-di-t-butylacetamidinate)ruthenium, it contains 59.2% of carbon, 10.4% of hydrogen and 13.8% of nitrogen.
- In the following examples, the resistivity was measured with the RT-80/RG-80 probe resistivity measuring instrument of Napson Co., Ltd. The film thickness and film density were measured with the X'Pert MRD grazing incidence X-ray analyzer of Philips Co., Ltd. The ESCA spectrum was measured with the JPS80 of JEOL Ltd. The adhesion was evaluated in accordance with a crosscut adhesion tape method specified in JIS K-5400.
- 0.01 g of tris (η3-N,N′-diisopropylacetamidinate)ruthenium obtained in Synthetic Example 1 was weighed and placed in a quartz boat type vessel in an argon gas, and the vessel was set in a quartz reactor. A quartz substrate was placed at a position near a gas stream in the reactor, and a nitrogen gas was passed into the reactor at room temperature at a flow rate of 250 ml/min for 30 minutes. Thereafter, a nitrogen gas was passed into the reactor at a flow rate of 100 ml/min, the inside pressure of the system was set to 1,333 Pa, and the reactor was heated at 180° C. for 30 minutes. Mist was generated from the boat type vessel, and a deposit on the quartz substrate installed nearby was seen. After the end of the generation of the mist, depressurization was stopped, a nitrogen gas was passed at 101.3 kPa at a flow rate of 200 ml/min, and the inside temperature of the reactor was raised to 350° C. and maintained at that temperature for 1 hour. Then, a film having a metallic gloss was obtained on the substrate. The thickness of this film was 100 Å.
- When the ESCA spectrum of this film was measured, peaks attributed to the Ru3d orbit were observed at 280 eV and 284 eV and no peak derived from another element was observed at all, which means that the film was made of metal ruthenium. When the resistivity of this ruthenium film was measured by the 4-terminal method, it was 38 μΩcm. The density of this film was 12.0 g/cm3. When the adhesion of this ruthenium film to the substrate was evaluated by a crosscut adhesion tape method, no separation between the substrate and the ruthenium film was seen at all.
- 0.01 g of (η3-N,N′-diisopropylacetamidinate)ruthenium dichloride obtained in Synthetic Example 2 was weighed and placed in a quartz boat type vessel in an argon gas, and the vessel was set in a quartz reactor. A quartz substrate was placed at a position near a gas stream in the reactor, and a nitrogen gas was passed into the reactor at room temperature at a flow rate of 250 ml/min for 30 minutes. Thereafter, a mixed gas of hydrogen and nitrogen (hydrogen content of 3 vol %) was passed into the reactor at a flow rate of 30 ml/min, the inside pressure of the system was set to 80 Pa, and the reactor was heated at 170° C. for 40 minutes. Mist was generated from the boat type vessel, and a deposit on the quartz substrate installed nearby was seen. After the end of the generation of the mist, depressurization was stopped, a mixed gas of hydrogen and nitrogen (hydrogen content of 3%) was passed at 101.3 kPa at a flow rate of 500 ml/min, and the inside temperature of the reactor was raised to 350° C. and maintained at that temperature for 1 hour. Then, a film having a metallic gloss was obtained on the substrate. The thickness of this film was 95 Å.
- When the ESCA spectrum of this film was measured, peaks attributed to the Ru3d orbit were observed at 280 eV and 284 eV and no peak derived from another element was observed at all, which means that the film was made of metal ruthenium. When the resistivity of this ruthenium film was measured by the 4-terminal method, it was 41 μΩcm. The density of this film was 11.6 g/cm3. When the adhesion of this ruthenium film to the substrate was evaluated by the crosscut adhesion tape method, no separation between the substrate and the ruthenium film was seen at all.
- 0.01 g of tris(η3-N,N′-di-t-butylacetamidinate)ruthenium obtained in Synthetic Example 3 was weighed and placed in a quartz boat type vessel in an argon gas, and the vessel was set in a quartz reactor. A quartz substrate was placed at a position near a gas stream in the reactor, and a nitrogen gas was passed into the reactor at room temperature at a flow rate of 250 ml/min for 30 minutes. Thereafter, a nitrogen gas was passed into the reactor at a flow rate of 100 ml/min, the inside pressure of the system was set to 1,333 Pa, and the reactor was heated at 170° C. for 30 minutes. Mist was generated from the boat type vessel, and a deposit on the quartz substrate installed nearby was seen. After the end of the generation of the mist, depressurization was stopped, a nitrogen gas was passed at 101.3 kPa at a flow rate of 200 ml/min, and the inside temperature of the reactor was raised to 350° C. and maintained at that temperature for 1 hour. Then, a film having a metallic gloss was obtained on the substrate. The thickness of this film was 98 Å.
- When the ESCA spectrum of this film was measured, peaks attributed to the Ru3d orbit were observed at 280 eV and 284 eV and no peak derived from another element was observed at all, which means that the film was made of metal ruthenium. When the resistivity of this ruthenium film was measured by the 4-terminal method, it was 40 μΩcm. The density of this film was 12.1 g/cm3. When the adhesion of this ruthenium film to the substrate was evaluated by the crosscut adhesion tape method, no separation between the substrate and the ruthenium film was seen at all.
- The procedure of Example 1 was repeated except that the amount of tris(η3-N,N′-diisopropylacetamidinate)ruthenium was changed to 0.005 g to obtain a 55 Å-thick film having a metallic gloss. When the ESCA spectrum of this film was measured, only peaks attributed to the Ru3d orbit were observed. The resistivity of this ruthenium film measured by the 4-terminal method was 48 μÚcm and the density of this film was 12.0 g/cm3. When the adhesion of this ruthenium film to the substrate was evaluated by the crosscut adhesion tape method, no separation between the substrate and the ruthenium film was seen at all.
- The procedure of Example 1 was repeated except that 0.01 g of commercially available bisethylcyclopentadienyl ruthenium was used in place of tris(η3-N,N′-diisopropylacetamidinate)ruthenium and the heating temperature of the reactor was changed to 300° C. to obtain a 220 Å-thick film having a metallic gloss. When the ESCA spectrum of this film was measured, only peaks attributed to the Ru3d orbit were observed, which means that this film was made of metal ruthenium. When the resistivity of this ruthenium film was measured by the 4-terminal method, it was 125 μΩcm. When the adhesion of this ruthenium film to the substrate was evaluated by the crosscut adhesion tape method, all the 100 squares were removed. The density of this film was 11.2 g/cm3.
- The procedure of Comparative Example 1 was repeated except that the amount of bisethylcyclopentadienyl ruthenium was changed to 0.005 g to obtain a film having a metallic gloss. The thickness of the obtained film was not uniform and varied from 60 to 190 Å. When the ESCA spectrum of this film was measured, only peaks attributed to the Ru3d orbit were observed. When the resistivity of this ruthenium film was measured by the 4-terminal method, it was 167 μΩcm, and the density of this film was 11.2 g/cm3. When the adhesion of this ruthenium film to the substrate was evaluated by the crosscut adhesion tape method, all the 100 squares were removed.
Claims (2)
1. A chemical vapor deposition material represented by the following formula (1):
Ru3+LnXmYl (1)
wherein L is a ligand represented by the following formula (2):
wherein R1, R2 and R3 are each independently a hydrogen atom, fluorine atom, trifluoromethyl group or hydrocarbon group having 1 to 10 carbon atoms,
X is a hydrogen anion, halogen anion, monovalent hydrocarbon anion having 1 to 10 carbon atoms or ligand represented by the following formula (3):
wherein R4, R5, R6, R7 and R8 are each independently a hydrogen atom, hydrocarbon group having 1 to 10 carbon atoms or trimethylsilyl group, with the proviso that when at least two out of R4, R5, R6, R7 and R8 are hydrocarbon groups having 1 to 10 carbon atoms, they may be bonded together to form a 4- to 8-membered ring,
Y is a ligand represented by the following formula (4):
wherein R9, R10, R12, R12, R13 and R14 are each independently a hydrogen atom or hydrocarbon group having 1 to 10 carbon atoms,
n is an integer of 1 to 3, m is an integer of 0 to 2, l is 0 or 1, and (n+m) is 3.
2. A method of forming a ruthenium film, which comprises subjecting the chemical vapor deposition material of claim 1 to chemical vapor deposition.
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Also Published As
Publication number | Publication date |
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TW200609238A (en) | 2006-03-16 |
TWI336704B (en) | 2011-02-01 |
JP4639686B2 (en) | 2011-02-23 |
KR20060046778A (en) | 2006-05-17 |
US7002033B1 (en) | 2006-02-21 |
JP2006037161A (en) | 2006-02-09 |
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