WO2017043620A1 - 有機ルテニウム化合物からなる化学蒸着用原料及び該化学蒸着用原料を用いた化学蒸着法 - Google Patents
有機ルテニウム化合物からなる化学蒸着用原料及び該化学蒸着用原料を用いた化学蒸着法 Download PDFInfo
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- WO2017043620A1 WO2017043620A1 PCT/JP2016/076585 JP2016076585W WO2017043620A1 WO 2017043620 A1 WO2017043620 A1 WO 2017043620A1 JP 2016076585 W JP2016076585 W JP 2016076585W WO 2017043620 A1 WO2017043620 A1 WO 2017043620A1
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- vapor deposition
- chemical vapor
- ruthenium
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- thin film
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- 150000003304 ruthenium compounds Chemical class 0.000 title claims abstract description 58
- 238000005229 chemical vapour deposition Methods 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims description 16
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 50
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000010409 thin film Substances 0.000 claims abstract description 48
- 239000003446 ligand Substances 0.000 claims abstract description 33
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 31
- 239000002994 raw material Substances 0.000 claims description 45
- 125000001424 substituent group Chemical group 0.000 claims description 38
- 229910052739 hydrogen Inorganic materials 0.000 claims description 20
- 239000001257 hydrogen Substances 0.000 claims description 20
- 239000007789 gas Substances 0.000 claims description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 15
- 239000000758 substrate Substances 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 125000004122 cyclic group Chemical group 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 6
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 239000010408 film Substances 0.000 abstract description 41
- 230000015572 biosynthetic process Effects 0.000 abstract description 25
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 abstract description 4
- 229910001882 dioxygen Inorganic materials 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 description 31
- 238000005755 formation reaction Methods 0.000 description 25
- 239000000126 substance Substances 0.000 description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 13
- 239000001301 oxygen Substances 0.000 description 13
- 229910052760 oxygen Inorganic materials 0.000 description 13
- 239000012495 reaction gas Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 125000004430 oxygen atom Chemical group O* 0.000 description 8
- 150000002430 hydrocarbons Chemical group 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- BXOGFPCKTBVDIA-UHFFFAOYSA-N [Ru+2].C(C)(C)N=CC=NC(C)C Chemical compound [Ru+2].C(C)(C)N=CC=NC(C)C BXOGFPCKTBVDIA-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 238000000151 deposition Methods 0.000 description 6
- 230000008021 deposition Effects 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000009834 vaporization Methods 0.000 description 6
- 230000008016 vaporization Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 150000001721 carbon Chemical group 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- KVJMACFFBNCRFH-UHFFFAOYSA-N [Ru].C(C)(C)N=CC=NC(C)C Chemical compound [Ru].C(C)(C)N=CC=NC(C)C KVJMACFFBNCRFH-UHFFFAOYSA-N 0.000 description 3
- 125000005595 acetylacetonate group Chemical group 0.000 description 3
- 238000000231 atomic layer deposition Methods 0.000 description 3
- 239000012159 carrier gas Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000005092 sublimation method Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000001004 secondary ion mass spectrometry Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- JFLCCNYEBDYEIR-UHFFFAOYSA-N CC(C)=CC(C)=C[Ru]C=C(C)C=C(C)C Chemical compound CC(C)=CC(C)=C[Ru]C=C(C)C=C(C)C JFLCCNYEBDYEIR-UHFFFAOYSA-N 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- VLTZUJBHIUUHIK-UHFFFAOYSA-N ethylcyclopentane;ruthenium Chemical compound [Ru].CC[C]1[CH][CH][CH][CH]1.CC[C]1[CH][CH][CH][CH]1 VLTZUJBHIUUHIK-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000011261 inert gas 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
- 239000007788 liquid Substances 0.000 description 1
- VXWPONVCMVLXBW-UHFFFAOYSA-M magnesium;carbanide;iodide Chemical compound [CH3-].[Mg+2].[I-] VXWPONVCMVLXBW-UHFFFAOYSA-M 0.000 description 1
- FRIJBUGBVQZNTB-UHFFFAOYSA-M magnesium;ethane;bromide Chemical compound [Mg+2].[Br-].[CH2-]C FRIJBUGBVQZNTB-UHFFFAOYSA-M 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
- 230000004792 oxidative damage Effects 0.000 description 1
- -1 pentadienyl group Chemical group 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- YAYGSLOSTXKUBW-UHFFFAOYSA-N ruthenium(2+) Chemical compound [Ru+2] YAYGSLOSTXKUBW-UHFFFAOYSA-N 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- 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
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
- C07C251/04—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C251/06—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of a saturated carbon skeleton
- C07C251/08—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of a saturated carbon skeleton being acyclic
-
- 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 Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0046—Ruthenium compounds
-
- 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
- C23C16/44—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 method of coating
-
- 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
Definitions
- the present invention relates to a raw material for chemical vapor deposition comprising an organic ruthenium compound for producing a ruthenium thin film or a ruthenium compound thin film by a chemical vapor deposition method (chemical vapor deposition method (CVD method), atomic layer deposition method (ALD method)).
- CVD method chemical vapor deposition method
- ALD method atomic layer deposition method
- the present invention relates to a raw material for chemical vapor deposition having a low decomposition temperature and appropriate thermal stability.
- Ruthenium or ruthenium compounds are used as thin film electrode materials for semiconductor devices such as DRAM and FERAM.
- a chemical vapor deposition method such as a CVD method (chemical vapor deposition method) or an ALD method (atomic layer vapor deposition method) is applied.
- CVD method chemical vapor deposition method
- ALD method atomic layer vapor deposition method
- raw material compounds used in such a chemical vapor deposition method those composed of many organic ruthenium compounds have been conventionally known.
- Patent Document 1 discloses bis (ethylcyclopentadienyl) ruthenium (II) shown in Chemical Formula 1 in which a cyclopentadienyl group which is a cyclic dienyl is coordinated. It is disclosed.
- Patent Document 2 discloses bis (2,4-dimethylpentadienyl) ruthenium (II) shown in Chemical Formula 2 in which a pentadienyl group which is a chain dienyl is coordinated.
- Patent Document 3 discloses benzene (glyoxal bisisopropylamine) ruthenium (II) represented by Chemical Formula 3, in which a benzene ring and a diazadiene group are coordinated to ruthenium.
- Patent Document 4 discloses dicarbonylbis (tetramethylheptanedionato) ruthenium shown in Chemical Formula 4 in which tetramethylheptanedionate and carbonyl are coordinated.
- the characteristics required for organic ruthenium compounds for chemical vapor deposition were mainly based on basic characteristics such as the availability of ruthenium thin films, efficiency, and handling.
- a raw material compound is vaporized to form a raw material gas, which is transported to a substrate.
- a compound having a high vapor pressure is suitable for efficient thin film formation.
- a material having high thermal stability and not easily decomposed is considered preferable.
- the above-described organic ruthenium compound represented by Chemical Formula 1 was a suitable organic ruthenium compound from an old viewpoint because of its high thermal stability in addition to its high vapor pressure. Furthermore, the fact that it is in a liquid state at room temperature has increased the usefulness of this organoruthenium compound. However, since this organoruthenium compound has a high decomposition temperature of 350 ° C., the film formation temperature cannot be set low.
- this organic ruthenium compound has a problem that ruthenium cannot be precipitated unless oxygen is introduced as a reaction gas.
- oxygen gas may oxidize a substrate made of silicon or the like, and there is a concern about the influence on device characteristics.
- the organic ruthenium compound of Chemical Formula 2 is also a compound that is solid at room temperature but is suitable from the viewpoint of vapor pressure. However, there is a problem in practical use because it is poor in thermal stability and easily decomposes even by heating at about 80 ° C. Furthermore, this organoruthenium compound also required oxygen as a reaction gas.
- the organic ruthenium compound of Chemical formula 3 can form a ruthenium thin film using hydrogen as a reactive gas, the problem of the reactive gas is cleared.
- this compound has a drawback that it has a low vapor pressure and is inferior in basic characteristics as a chemical vapor deposition raw material.
- the high or low vapor pressure is a characteristic related to the efficiency of film formation, and is a condition that cannot be removed from the viewpoint of industrial utilization of chemical vapor deposition.
- the organic ruthenium compounds of Chemical Formulas 4 and 5 can be applied with hydrogen as a reaction gas, there is a concern that oxygen atoms are included in the structure of the ligand.
- oxygen atoms of the ligand may be mixed into the ruthenium thin film. It is thought that oxygen in the ruthenium thin film affects the electrode characteristics.
- the oxygen incorporation into the thin film is mentioned in Patent Document 4, and it is clear that the ruthenium thin film produced by the compound of Chemical Formula 4 contains about 3% oxygen.
- the organic ruthenium compound of Chemical Formula 4 is also a compound that is difficult to be applied to low-temperature film formation, and requires a considerably high film formation temperature of 400 ° C. or higher.
- the present invention provides an organoruthenium compound that can be used for low-temperature film formation while having basic characteristics as a raw material for chemical vapor deposition.
- the present invention provides an organic ruthenium compound which can produce a ruthenium thin film without using oxygen gas and hardly affects the substrate and the ruthenium thin film to be produced.
- a specific guideline for low-temperature film formation is that film formation at 250 ° C. or lower is possible.
- the present invention which solves the above-mentioned problems is a raw material for chemical vapor deposition for producing a ruthenium thin film or a ruthenium compound thin film by chemical vapor deposition.
- Ruthenium has two diazadiene ligands and two alkyls represented by the following formula: It is a raw material for chemical vapor deposition comprising an organic ruthenium compound coordinated with a ligand.
- the substituents R 1 to R 8 of the diazadiene ligand are hydrogen or a hydrocarbon group having 1 to 4 carbon atoms.
- Two or more substituents selected from the substituents R 1 to R 4 are And may form a cyclic structure together with the carbon atom or nitrogen atom to which they are directly bonded, and two or more substituents selected from the substituents R 5 to R 8 are also bonded to each other, and A cyclic structure may be formed with a carbon atom or a nitrogen atom directly bonded to each other.
- Substituents R 9 and R 10 which are alkyl ligands are alkyl groups having 1 to 3 carbon atoms.
- the raw material for chemical vapor deposition of the present invention comprises an organic ruthenium compound having both a diazadiene ligand and an alkyl ligand.
- the reason why these ligands are applied is that the thermal stability is set to an appropriate range in consideration of the strength of the binding of each ligand to ruthenium, and low temperature film formation under a hydrogen atmosphere is possible. . That is, a diazadiene-ruthenium bond having a strong bonding force and an alkyl-ruthenium bond having a relatively weak bonding force are introduced into the structure of the organic ruthenium compound to control the physical properties of the entire compound.
- This organic ruthenium compound is composed of a diazadiene ligand composed of nitrogen, carbon and hydrogen, an alkyl ligand composed of carbon and hydrogen, and ruthenium and does not contain an oxygen atom. Therefore, the ruthenium thin film to be formed does not contain oxygen derived from the raw material and does not oxidize the substrate.
- the organic ruthenium compound applied in the present invention has an appropriately high vapor pressure, which is a basic characteristic required as a raw material for chemical vapor deposition. This is because the substituents R 1 to R 8 of the diazadiene ligand are hydrogen or a hydrocarbon group having 1 to 4 carbon atoms, and the alkyl ligands R 9 and R 10 have 1 to 3 carbon atoms. By limiting to relatively short chain alkyl groups.
- the substituents R 1 to R 8 in the diazadiene ligand are hydrogen or a hydrocarbon group having 1 to 4 carbon atoms. All of the substituents R 1 to R 8 may be hydrogen, and at least one of the substituents R 1 to R 8 may be a hydrocarbon group.
- the hydrocarbon group is a substituent composed of hydrogen and carbon.
- the substituents R 1 to R 8 in the diazadiene ligand are limited to 1 or more and 4 or less carbon atoms because the carbon chain of these substituents R 1 to R 8 is not limited to the vapor pressure of the organic ruthenium compound. It is because it can affect. If the carbon number is excessively large, the vapor pressure may be lowered.
- substituent R 1 ⁇ R 8 hydrocarbon group examples of these substituents linear or branched alkyl group, a vinyl group, an allyl group and the like.
- substituents R 1 to R 8 are hydrocarbon groups, they may be independent substituents or may be bonded to each other. That is, two or more substituents selected from the substituents R 1 to R 4 may be bonded to each other to form a cyclic structure together with the carbon atom or nitrogen atom to which they are directly bonded. Similarly, two or more substituents selected from the substituents R 5 to R 8 may be bonded to each other to form a cyclic structure together with the carbon atom or nitrogen atom to which they are directly bonded.
- an organic ruthenium compound coordinated by a diazadiene ligand having a cyclic substituent as described below is also within the scope of the present invention.
- At least one of the substituents R 1 , R 4 , R 5 , and R 8 is an alkyl group, and at least one of the alkyl groups has 1 or more carbon atoms. 4 or less linear or branched alkyl groups. All of the substituents R 1 , R 4 , R 5 , and R 8 may be alkyl groups having 1 to 4 carbon atoms, but some of the substituents of R 1 , R 4 , R 5 , and R 8 are The alkyl group having 1 to 4 carbon atoms and the other substituent may be hydrogen or another alkyl group.
- linear or branched alkyl group examples include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, and a tert-butyl group.
- R 2 , R 3 , R 6 , and R 7 when at least any one of the substituents R 2 , R 3 , R 6 , and R 7 is an alkyl group, it is preferable that at least one of the alkyl groups is a methyl group.
- R 2 , R 3 , R 6 , and R 7 may all be methyl groups, but some of R 2 , R 3 , R 6 , and R 7 are methyl groups and the other substituents are hydrogen. Alternatively, other alkyl groups may be used.
- the other ligand is an alkyl group having 1 to 3 carbon atoms (methyl group, ethyl group, n-propyl group, iso-propyl group).
- the length of the carbon chain of the alkyl ligand affects the level of vapor pressure of the organoruthenium compound. By limiting this ligand to a short-chain alkyl group, a suitable vapor pressure can be secured.
- the chemical vapor deposition method of the ruthenium thin film or ruthenium compound thin film to which the chemical vapor deposition material according to the present invention is applied will be described.
- the raw material composed of the organic ruthenium compound described above is vaporized by heating to generate a raw material gas, and the raw material gas is transported onto the substrate surface to heat the organic ruthenium compound.
- the ruthenium thin film is formed by decomposition.
- the organic ruthenium compound applied in the present invention may be in a solid state at room temperature, but has a high vapor pressure and can be easily vaporized by the sublimation method. Therefore, the organic ruthenium compound as a raw material can be heated as it is.
- the raw material gas can be obtained by dissolving in an appropriate solvent and heating the solution. The heating temperature of the raw material is preferably 50 ° C. or higher and 150 ° C. or lower.
- Vaporized raw material is usually combined with a carrier gas and transported onto a substrate.
- the organic ruthenium compound of the present invention can be formed into ruthenium without using a reactive gas using an inert gas (argon, nitrogen, etc.) as a carrier gas.
- an inert gas argon, nitrogen, etc.
- the reaction gas can be set appropriately.
- the raw material for chemical vapor deposition according to the present invention can be formed without using oxygen when producing a thin film made of ruthenium.
- reducing gas species such as hydrogen, ammonia, hydrazine, and formic acid can be used as the reaction gas.
- application of oxygen as a reactive gas is not avoided.
- oxygen gas can be used as a reaction gas.
- These reaction gases can also serve as a carrier gas.
- the film formation temperature during film formation is preferably 150 ° C. or higher and 500 ° C. or lower. If the temperature is lower than 150 ° C., the film formation reaction does not proceed easily, and efficient film formation cannot be performed. In addition, when the temperature is too high, uniform film formation becomes difficult, and there is a problem that the substrate may be damaged.
- This film forming temperature is usually adjusted by the heating temperature of the substrate. However, considering the achievement of low-temperature film formation, which is an object of the present invention, the film formation temperature is more preferably 150 ° C. or higher and 400 ° C. or lower, and more preferably 150 ° C. or higher and 300 ° C. or lower.
- the organic ruthenium compound constituting the chemical vapor deposition raw material according to the present invention has thermal stability in a range required for the chemical vapor deposition raw material by selecting a ligand coordinated to ruthenium.
- the organoruthenium compound of the present invention has an intermediate stability between the compound of Chemical Formula 2 and the compound of Chemical Formula 3 (Chemical Formula 3> Compound of the Present Application> Chemical Formula 2), and is used as a raw material for chemical vapor deposition. It is reasonably stable to handle.
- the vapor pressure is also a suitable height by adjusting the ligand and its substituent.
- the raw material for chemical vapor deposition according to the present invention can form a ruthenium thin film by applying a reaction gas other than oxygen such as hydrogen. Further, the constituent elements of the compound do not contain oxygen atoms. Therefore, there is no mixing of oxygen atoms into the manufactured ruthenium thin film, and there is no fear of oxidative damage of the substrate.
- the raw material for chemical vapor deposition according to the present invention is useful for forming electrodes of semiconductor devices that have been highly miniaturized in recent years.
- the organic ruthenium compound produced above was subjected to physical property evaluation and film formation test.
- TG-DTA Differential thermal-thermogravimetric measurement
- a ruthenium thin film was formed by a CVD apparatus (hot wall type CVD film formation apparatus) using the organic ruthenium compound according to the present embodiment as a raw material.
- the film forming conditions are as follows.
- Substrate Ta / TH-Ox / Si (thermally oxidized Si + Ta) Deposition temperature: 250 ° C, 300 ° C Sample temperature (vaporization temperature): 95 ° C Pressure: 5 torr Gas: Hydrogen or argon gas Gas flow rate: 20 sccm Deposition time: 60 min
- the ruthenium thin film was formed by changing the film forming temperature and the reaction gas, and the film thickness and the oxygen concentration in the thin film were measured.
- the film thickness of the ruthenium thin film the film thickness at a plurality of locations was measured from the observation result by SEM (scanning electron microscope), and the average value was calculated.
- the oxygen concentration was measured by SIMS (secondary ion mass spectrometry: ADEPT-1010 manufactured by ULVAC-PHI). The results are shown in Table 1.
- Test No. 1 and no From the result of 2, it was confirmed that the ruthenium thin film can be formed even when the film forming temperature is set to a low temperature of 250 ° C. In addition, it can be seen that the film can be formed even when hydrogen is used as the reaction gas, and the film can be formed using argon as well. And test no. 3 and no. As shown in FIG. 4, even when the film was formed at a relatively high temperature of 300 ° C., oxygen was not detected from the ruthenium thin film. 3 and 4 show SEM photographs of the ruthenium thin film formed at a film forming temperature of 250 ° C.
- Comparative Example A ruthenium thin film was produced using tris (acetylacetonato) ruthenium of the above chemical formula 5 as a raw material.
- the conditions were as follows. In the case of the comparative example, since it was predicted that the film could not be formed at 300 ° C. or lower, the film was formed at 400 ° C. and 500 ° C. The results of this film formation test are shown in Table 2.
- Substrate Ta / TH-Ox / Si (Ta / thermally oxidized Si) Deposition temperature: 250 ° C, 300 ° C, 400 ° C, 500 ° C, Sample temperature (vaporization temperature): 140 ° C Pressure: 5 torr Reaction gas: Hydrogen reactive gas flow rate: 20 sccm Deposition time: 15 min
- Second Embodiment In this embodiment, as the organic ruthenium compound, cis-diethyl-bis (N, N′-diisopropyl-1,4-diaza-1,3-butadiene) ruthenium (II) (substituent R 1 , R 4 , R 5 and R 8 are all iso-propyl groups, and R 9 and R 10 are all ethyl groups).
- the change in weight by TG-DTA analysis was measured under atmospheric pressure conditions.
- the analysis conditions were the same as in the first embodiment.
- the result is shown in FIG. In FIG. 5, the weight change is also shown for comparison with the compound of the first embodiment. From FIG. 5, it can be confirmed that the organoruthenium compound of the second embodiment also decomposes smoothly in the atmosphere.
- the organic ruthenium compound cis-diethyl-bis (N, N′-diisopropyl-1,4-diaza-1,3-butadiene) ruthenium (II) is the same as the organic ruthenium compound of the first embodiment. Compared with cis-dimethyl-bis (N, N′-diisopropyl-1,4-diaza-1,3-butadiene) ruthenium (II), it can be seen that the compound can be decomposed at a lower temperature. This organoruthenium compound can be expected to be used for film formation at a lower temperature.
- the raw material for chemical vapor deposition according to the present invention has a high thermal stability of the constituent organic ruthenium compound and an appropriate vapor pressure, and is excellent in film forming property at a low temperature. Also, ruthenium can be formed using hydrogen or the like as a reactive gas.
- the present invention is suitable for use as a thin film electrode material for semiconductor devices such as DRAM and FERAM.
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Abstract
Description
成膜温度:250℃、300℃
試料温度(気化温度):95℃
圧力:5torr
ガス:水素又はアルゴンガス
ガス流量:20sccm
成膜時間:60min
成膜温度:250℃、300℃、400℃、500℃、
試料温度(気化温度):140℃
圧力:5torr
反応ガス:水素
反応ガス流量:20sccm
成膜時間:15min
Claims (4)
- 化学蒸着法によりルテニウム薄膜又はルテニウム化合物薄膜を製造するための化学蒸着用原料において、
次式で示される、ルテニウムに2つのジアザジエン配位子、及び、2つのアルキル配位子が配位した有機ルテニウム化合物からなる化学蒸着用原料。
- 置換基R1、R4、R5、R8の少なくともいずれかがアルキル基であり、前記アルキル基の少なくともいずれかが炭素数1以上4以下の直鎖若しくは分岐鎖のアルキル基である請求項1に記載の化学蒸着用原料。
- 置換基R2、R3、R6、R7の少なくともいずれかがアルキル基であり、前記アルキル基の少なくともいずれかがメチル基である請求項1又は請求項2に記載の化学蒸着用原料。
- 有機ルテニウム化合物からなる原料を気化して原料ガスとし、前記原料ガスを基板表面に導入しつつ加熱するルテニウム薄膜又はルテニウム化合物薄膜の化学蒸着法において、
前記原料として請求項1~請求項3のいずれかに記載の化学蒸着用原料を用いる化学蒸着法。
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US15/754,740 US20180258526A1 (en) | 2015-09-11 | 2016-09-09 | Chemical vapor deposition raw material including organoruthenium compound and chemical deposition method using the chemical vapor deposition raw material |
EP16844481.8A EP3348667A4 (en) | 2015-09-11 | 2016-09-09 | Chemical vapor deposition feedstock comprising organic ruthenium compound and chemical vapor deposition method using said chemical vapor deposition feedstock |
KR1020187007309A KR102123451B1 (ko) | 2015-09-11 | 2016-09-09 | 유기 루테늄 화합물을 포함하는 화학 증착용 원료 및 그 화학 증착용 원료를 사용한 화학 증착법 |
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CN112292383A (zh) * | 2018-07-27 | 2021-01-29 | 优美科股份公司及两合公司 | 金属有机化合物 |
WO2023008248A1 (ja) * | 2021-07-29 | 2023-02-02 | 株式会社Adeka | 反応性材料及び薄膜の製造方法 |
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JP6912913B2 (ja) * | 2017-03-29 | 2021-08-04 | 株式会社Adeka | 原子層堆積法による酸化イットリウム含有薄膜の製造方法 |
WO2019017285A1 (ja) * | 2017-07-18 | 2019-01-24 | 株式会社高純度化学研究所 | 金属薄膜の原子層堆積方法 |
JP7148377B2 (ja) * | 2018-12-03 | 2022-10-05 | 田中貴金属工業株式会社 | ルテニウム錯体からなる化学蒸着用原料及び該化学蒸着用原料を用いた化学蒸着法 |
KR102519909B1 (ko) | 2020-10-08 | 2023-04-11 | (주)원익머트리얼즈 | 신규한 루테늄 화합물, 이의 제조방법, 이를 포함하는 박막 형성용 원료, 및 이를 이용하여 고순도 루테늄 박막을 형성하는 방법 |
JP7075518B1 (ja) * | 2021-03-10 | 2022-05-25 | 田中貴金属工業株式会社 | 有機ルテニウム化合物を含む化学蒸着用原料及びルテニウム薄膜又はルテニウム化合物薄膜の化学蒸着法 |
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- 2016-09-09 EP EP16844481.8A patent/EP3348667A4/en not_active Withdrawn
- 2016-09-09 KR KR1020187007309A patent/KR102123451B1/ko active IP Right Grant
- 2016-09-09 US US15/754,740 patent/US20180258526A1/en not_active Abandoned
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WO2013117955A1 (en) * | 2012-02-07 | 2013-08-15 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Method for the deposition of a ruthenium containing film using arene diazadiene ruthenium(0) precursors |
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WO2023008248A1 (ja) * | 2021-07-29 | 2023-02-02 | 株式会社Adeka | 反応性材料及び薄膜の製造方法 |
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KR20180040673A (ko) | 2018-04-20 |
TW201723209A (zh) | 2017-07-01 |
KR102123451B1 (ko) | 2020-06-16 |
JP2017053019A (ja) | 2017-03-16 |
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US20180258526A1 (en) | 2018-09-13 |
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